Processes for the production of tri-organo-monoalkoxysilanes and process for the production of tri-organo-monochlorosilanes

ABSTRACT

A silane containing a bulky hydrocarbon group or groups R therein and having the formula (III)
 
R 3−(x+y) (R 1 ) x (R 2 ) y Si(OR 3 )
 
can be produced by reacting a silane of the formula (I)
 
(R 1 ) x (R 2 ) y SiCl 3−(x+y) (OR 3 )
 
with a Grignard reagent of the formula (II)
 
RMgX
 
Further, a tri-organo-chlorosilane of the formula (XIIa)
 
(R 1 )(R 2 )(R 3 )SiCl
 
can be produced by reacting a tri-organo-silane of the formula (XIa)
 
(R 1 )(R 2 )(R 3 )SiZ 1  
 
with hydrochloric acid.
 
     Furthermore, a tri-organo-monoalkoxysilane of the formula (XXIII)
 
R 3−(x+y) (R 1 ) x (R 2 ) y Si(OR 3 )
 
can be produced when a silane of the formula (XXI)
 
(R 1 ) x (R 2 ) y SiCl 4−(x+y)  
 
is reacted with a Grignard reagent of the formula (XXII)
 
RMgX
 
with addition of and reaction with an alcohol or an epoxy compound during the reaction.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No.10/495,075, filed Nov. 12, 2004, now U.S. Pat. No. 7,459,577, which is a371 application based on PCT/JP02/11694, filed Nov. 8, 2002,incorporated herein by reference.

TECHNICAL FIELD

This invention relates to a novel process capable of producing, easilyand effectively, a tri-organo-mono-(substituted or unsubstitutedalkoxy)silane containing therein at least two bulky hydrocarbon groupslikely to easily bring about a steric hindrance, such as a secondary ortertiary hydrocarbon group, including secondary or tertiary alkylgroups. The aforesaid silane may be useful for the production of awater-repellent and also for the production of a hydroxyl-protectingagent of silyl type for the protection of functional hydroxyl groupspresent in chemical intermediates formed in the organic syntheses.

This invention further relates to a novel process capable of producing,advantageously and easily on an industrial scale, atri-organo-monochlorosilane, particularly a tri-organo-monochlorosilanecontaining therein a bulky hydrocarbon group or groups, such as asecondary or tertiary hydrocarbon group. Thetri-organo-monochlorosilanes may be utilized as materials for thesynthesis of silicone rubber and also as a silylating agent forprotecting functional hydroxyl groups in the chemical intermediatesformed in the organic syntheses done in the synthesis of medicines,agricultural chemicals and others.

BACKGROUND ART

As the methods for introducing organic groups (that is, organo-groups)such as an alkyl group, an aralkyl group or an aryl group or the likeinto silicon compounds, there is now generally employed such processwherein a Grignard reagent containing said organic group is reacted withan organo-substituted or organo-unsubstituted chlorosilane containingone to four chloro groups, thereby to produce an organo-silanecontaining one to four organo groups and also zero to three chlorogroups. However, a bulky, secondary or tertiary hydrocarbon group likelyto easily bring about a steric hindrance is not readily introducibleinto the said organo-substituted or organo-unsubstituted chlorosilanecontaining one to four chloro groups, by means of the process comprisingreacting the Grignard reagent containing such bulky hydrocarbon groupwith said organo-substituted or organo-unsubstituted chlorosilane.

There is also known another process wherein a secondary or tertiaryalkyl lithium is used, instead of such Grignard reagent, and is reactedwith said organo-substituted or organo-unsubstituted chlorosilane (referto J. Org. Chem. Vol. 43, p. 3649 (1978)).

For a process for the introduction of a secondary hydrocarbon group or atertiary hydrocarbon group likely to easily cause the steric hindrance,onto a silicon atom of an organo-halosilane by means of the Grignardreaction, there is also known a process wherein a Grignard reagentcontaining a secondary or tertiary hydrocarbon group is reacted with theorgano-halosilane in the presence of a catalyst comprising a coppercompound or a cyanide compound or thiocyanic acid compound (refer toJapanese Patent Publication Hei-7-86115, Japanese Patent No. 2838342 andJapanese Patent No. 2854832).

Further, there is known a process for the synthesis of adimethyl-monoalkoxy-arylsilane and adimethyl-monoalkoxy-cyclohexylsilane, comprising reacting adimethyl-monoalkoxy-chlorosilane with a Grignard reagent containingphenyl group, 1-naphthyl group or cyclohexyl group (refer to Zh. Obshch.Khim., 1987, 57(1), pp. 146-151 and Chemical Abstracts, Vol. 108, Par.6072v). However, the Russian literature above-mentioned has nodescription of the production of a tri-organo-monoalkoxysilanecontaining at least two of the bulky hydrocarbon groups.

There is known an organo-hydrosilane compound having a silicon-hydrogenlinkage, and there is also known a process comprising reacting suchorgano-hydrosilane compound with a Grignard reagent containing atertiary hydrocarbon group (refer to Japanese Patent No. 3091992).

Further, there are many known processes for the production oftri-organo-monochlorosilanes containing a bulky hydrocarbon group. Mainknown processes proposed for such purpose are as follows.

-   (1) Process comprising reacting an organo-halosilane with a Grignard    reagent in the presence of a catalyst to cause a Grignard reaction    to produce a tri-organo-monochlorosilane intended, filtering the    resulting reaction solution to remove therefrom the magnesium    chloride deposited, and recovering the intended silane product    (Japanese Patent Publication Hei-7-86115).-   (2) Process according to the process (1) above, wherein the reaction    solution resulting from the Grignard reaction is subjected directly    to a distillation after the Grignard reaction was conducted with    using a solvent made of polyalkyleneglycol dialkylether (Japanese    Patent No. 2854832).-   (3) Commercially available process adapted for industrial scale    production, wherein the silicon-hydrogen linkage of a    tri-organo-hydrosilane is chlorinated with chlorine.-   (4) Process wherein the alkoxy group of a tri-organo-alkoxysilane is    chlorinated with a chlorinating agent such as an acyl chloride,    thionyl chloride, phosphorus trichloride, and the like.-   (5) Process wherein the chlorination of a tri-organo-hydrosilane is    effected by an exchange reaction between a tri-organo-hydrosilane    and a chlorosilane in the presence of a catalyst (Japanese Patent    No. 3131868).-   (6) Process wherein a tri-organo-hydrosilane is reacted with    hydrogen chloride gas in the presence of a transition metal of Group    VIII or a complex thereof under anhydrous condition (Japanese Patent    Prepublication Kokai Hei-6-157554).-   (7) Process as described in J. Am. Chem. Soc., Vol. 68, p. 2282    (1946), wherein triethylsilanol is treated with a conc. hydrochloric    acid under ice-cooling, thereby to afford triethylchlorosilane in    77% yield.-   (8) Process as described in a book “Chemistry and Technology of    Silicones”, Page 86, (published in 1968 by ACADEMIC PRESS), wherein    a trialkylalkoxysilane is treated with hydrogen chloride gas under    anhydrous condition and converted into the corresponding    chlorosilane.

However, in the above process (1) according to Japanese PatentPublication Hei-7-86115, the operation for the removal by filtration ofthe magnesium chloride by-produced is troublesome, with needs ofadditional treatment of magnesium chloride. In the process (2) aboveaccording to Japanese Patent No. 2854832, the use of the special solventis necessary, so that this process is disadvantageous commercially inview of expensive cost. In the commercial process shown in (3) above, achlorinated solvent is required as the reaction solvent, so that thereis a serious problem for the environmental protections. In thechlorination process shown in (4) above, the generation of sulfurdioxide gas and other by-products is involved and is problematic in viewof the environmental protections. In the process (5) above according toJapanese Patent No. 3131868, the inevitable formation of unnecessaryby-products and the use of the catalyst are disadvantageous ineconomical point of view.

In the above process (6) according to Japanese Patent PrepublicationKokai Hei-6-157554, the use of expensive metal catalyst is required andthus not advantageous in industrial operations. In the process (7) aboveaccording to the report of J. Am. Chem. Soc., Vol. 68, p. 2282 (1946),the silanol compound is to be treated with conc. hydrochloric acid underice-cooling conditions, because the silanol is easily hydrolyzable andis difficult to be handled, so that the industrial practice of thisprocess is not advantageous in economical point of view. The process (8)above according to “Chemistry and Technology of Silicones”, p. 86, wherethe chlorination is to be effected with hydrogen chloride gas underanhydrous conditions, is still needed to be improved upon its industrialpractice in respect of the safety and the operating efficiency, due tothe necessary handling of hydrogen chloride gas. In consequence, all theknown processes proposed in the prior art have some unavoidable defects.

Accordingly, there is a keen demand for creating any novel industrialprocess for the production of organo-chlorosilanes, which is able towork more easily and simply in a commercial scale.

For the purpose of producing the organosilanes containing a secondary ortertiary alkyl group or groups, the above-mentioned prior art process asshown in J. Org. Chem., Vol. 43, p. 3649 shall require that theorgano-substituted or organo-unsubstituted chlorosilane is reacted witha secondary or tertiary alkyl lithium. This prior art process cannot besuitable if it is applied on an industrial scale operation with handlingof a large amount of materials, because the handlings of metalliclithium and of alkyl lithium as prepared therefrom are very dangerous.

In cases of the prior art processes as taught by Japanese PatentPublication Hei-7-86115, Japanese Patent No. 2838342 or Japanese PatentNo. 2854832, these processes shall require that a Grignard reaction iscarried out by using the catalyst made of a copper compound, a cyanidecompound or a thiocyanate compound. In these processes, the use ofhighly toxic compounds as the catalyst is required, thus bringing aboutproblems on safety. In the another prior art process shown in JapanesePatent No. 3091992, an organo-hydrosilane compound having asilicon-hydrogen linkage is used as the starting material, and thisstarting material is often expensive. Further, in the other process ofthe prior art where a trichlorosilane is to be used as the startingmaterial, the starting material is a low boiling, inflammable substance,so that special caution is required for handling it, thus causingproblems on safety and economy.

Therefore, it is now keenly required to provide any novel process forproducing a tri-organo-monoalkoxysilane compound having at least twobulky hydrocarbon groups each likely to cause the steric hindrance, suchas a secondary or tertiary alkyl group, which process can be operated ina facile way on industrial scale, safely and in a high yield.

DISCLOSURE OF THE INVENTION

We, the inventors of this invention, have eagerly proceeded ourinvestigations with the intention of producing atri-organo-monoalkoxysilane having at least two bulky hydrocarbon groupstherein. As a result, we have now confirmed that, in case whentetrachlorosilane (namely, silicon tetrachloride) is subjected to aGrignard reaction with isopropyl magnesium chloride as Grignard reagent,for example, in a usual manner and under usual reaction conditions, thedesired Grignard reaction expectedly can hardly progress to an extentthat the desired tri(isopropyl)-monochlorosilane can be produced.

Apart from the fact we have confirmed in the above, however, we have nowfound, for the first time, that the desired tri-(isopropyl)-monomethoxy,monoethoxy or mono-n-butoxysilane can be produced in a high yield, iftetrachlorosilane is reacted at first with methanol, ethanol orn-butanol to replace one of the four chloro groups of tetrachlorosilaneby methoxy, ethoxy or n-butoxy group, to produce monomethoxy, monoethoxyor mono-n-butoxytrichlorosilane, and if the resultingmonoalkoxy-trichlorosilane so produced is then contacted and reactedwith isopropyl magnesium chloride in a usual manner and under usualreaction conditions for the Grignard reaction, to result in that thedesired Grignard reaction can progress efficiently to attain theintended result. We have now further found that the above-mentionedreaction procedure, has no need to use any catalyst and no need toprovide the presence of a copper compound, cyanide compound orthiocyanate compound for effecting the progress and achievement of theintended Grignard reaction.

We now have furthermore found that the desired Grignard reaction canalso proceed efficiently when tetrachlorosilane is at first reactedwith, for example, ethylene oxide or benzyl alcohol and when theresulting mono(2-chloroethoxy)-trichlorosilane ormonobenzyloxytrichlorosilane so produced is then subjected to theGrignard reaction, for example, with using isopropyl magnesium chlorideor sec-butyl magnesium chloride as the Grignard reagent, in a usualmanner and under usual reaction conditions for the Grignard reaction,and that the desired tri-(isopropyl or sec-butyl)-mono(2-chloroethoxy orbenzyloxy)silane can thus be produced in a high yield. In addition, wehave found that the tri-(isopropyl)-monomethoxy, monoethoxy ormono-n-butoxysilane, as well as the tri-(isopropyl orsec-butyl)-mono(2-chloroethoxy or benzyloxy)silane as produced in theabove Grignard reaction can then be converted into tri-(isopropyl orsec-butyl)-monochlorosilane, if it is treated by a known chlorinatingmethod, for example, with a chlorinating agent such as thionyl chloride.

The latter compound, tri-(isopropyl or sec-butyl)-monochlorosilane, isknown as a hydroxyl-protecting agent of silyl type to protect afunctional hydroxyl group of chemical intermediate compounds usable inorganic syntheses and also is known as a useful starting material forthe production of various water-repellents of silicone type.

We have proceeded our further investigations. As a result, we have nowfound generically that an organo-unsubstituted or a mono-organo ordi-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)-tri, di ormonochlorosilane having the general formula (I)(R¹)_(x)(R²)_(y)SiCl_(3−(x+y))(OR³)  (I)wherein R¹ stands for a primary, secondary or tertiary alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an aryl group oran aralkyl group, R² stands for a secondary alkyl group, a tertiaryalkyl group, a cycloalkyl group or an aryl group, and R³ stands for aprimary or secondary alkyl group, a cycloalkyl group or an aralkylgroup, or the group —OR³ stands for a 2-substituted orunsubstituted-2-chloroethoxy group of the formula (A)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms or R⁴is an alkoxymethylene group or an alkenyloxymethylene group or anaryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group, particularly phenyl group ornaphthyl group, and x stands for an integer of 0 or 1, and y stands foran integer of 0, 1 or 2, provided that the integers for x and y are tobe within the range of 0≦(x+y)≦2, is able to easily react with aGrignard reagent of the general formula (II)RMgX  (II)wherein R stands for a secondary alkyl group, a tertiary alkyl group ora cycloalkyl group, or R stands for an alkyl-substituted aromatichydrocarbon group of which the alkyl substituent is bonding to a carbonatom present in the aromatic hydrocarbon group with said carbon atombeing adjacent to the carbon atom of the aromatic hydrocarbon group thatis bonding to the magnesium atom, and X stands for a chlorine, bromineor iodine atom, in a usual manner and under usual reaction conditionsfor the Grignard reaction, and without the necessity of adding anycatalyst in the reaction system; and that there can thus be produced atri-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)silane containingthe bulky hydrocarbon group or groups R therein and having the generalformula (III)R_(3−(x+y))(R¹)_(x)(R²)_(y)Si(OR³)  (III)wherein R¹, R², R³ have the same meanings as defined above, R is thesecondary alkyl group, tertiary alkyl group or cycloalkyl group asdefined above or the alkyl-substituted aromatic hydrocarbon group asdefined above, and x and y stand for the above-defined integers.

It is presumed that the chloro group, which is bonding to the siliconatom of the silane via the silicon-chlorine linkage present in theorgano-unsubstituted or mono-organo- or di-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)-tri, di or monochlorosilane of the generalformula (I), has got an increased reactivity to the bulky hydrocarbongroup due to certain function of the alkoxy group, cycloalkyloxy groupor aralkyloxy group OR³ existing in said silane of the formula (I).

According to a first aspect of this invention, therefore, there isprovided a process for the production of a tri-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)silane containing a bulky hydrocarbon groupor groups R therein and having the general formula (III)R_(3−(x+y))(R¹)_(x)(R²)_(y)Si(OR³)  (III)wherein R¹ stands for a primary, secondary or tertiary alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an aryl group oran aralkyl group, R² stands for a secondary alkyl group, a tertiaryalkyl group, a cycloalkyl group or an aryl group, and R³ stands for aprimary or secondary alkyl group, a cycloalkyl group or an aralkylgroup, or the group —OR³ stands for a 2-substituted orunsubstituted-2-chloroethoxy group of the formula (A)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, or R⁴is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group, and wherein R stands for asecondary alkyl group, a tertiary alkyl group or a cycloalkyl group, orR is an alkyl-substituted aromatic hydrocarbon group as defined below,and x stands for an integer of 0 or 1 and y stands for an integer of 0,1 or 2, provided that these integers for x and y are to be within therange of 0≦(x+y)≦2, characterized in that the process comprises reactingan organo-unsubstituted or mono-organo or di-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)-tri, di or monochlorosilane of the generalformula (I)(R¹)_(x)(R²)_(y)SiCl_(3−(x+y))(OR³)  (I)wherein R¹, R², R³, x and y have the same meanings as defined above,with a Grignard reagent of the general formula (II)RMgX  (II)wherein R stands for a secondary alkyl group, a tertiary alkyl group ora cycloalkyl group as defined above, or R stands for analkyl-substituted aromatic hydrocarbon group of which the alkylsubstituent is bonding to a carbon atom present in the aromatichydrocarbon group, with said carbon atom being adjacent to the carbonatom of the aromatic hydrocarbon group that is bonding to the magnesiumatom, and X stands for a chlorine, bromine or iodine atom.

The above process of the first aspect of this invention will now beexplained in detail.

First of all, the explanation is given on the following three methods(i)-(iii) for preparing the organo-unsubstituted or mono-organo ordi-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)-tri, di ormonochlorosilane of the general formula (I) which is to be used as thestarting compound in the process of the first aspect of this invention.

Method (i): The organo-unsubstituted or mono-organo ordi-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)-tri, di ormonochlorosilane of the general formula (I) to be used as the startingcompound, where group —OR³ in the formula (I) does not mean the2-substituted or unsubstituted-2-chloroethoxy group of the formula (A),may be prepared by reacting tetrachlorosilane or a di or mono-organo-dior trichlorosilane of the general formula (IV)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (IV)wherein R¹ and R² have the same meanings as defined above and x and yare integers as defined above, with an alcohol of the general formula(V)R³OH  (V)wherein R³ stands for the primary or secondary alkyl group, cycloalkylgroup or aralkyl group as defined above.

The tetrachlorosilane is the compound of the formula (B)

which is included in the compounds of formula (IV) above (namely, thecase of x=y=0).

The substituent R¹ in the compound of the general formula (IV) above isa primary, secondary or tertiary alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an aryl group or an aralkyl group.

The primary, secondary or tertiary alkyl group for R¹ is preferably astraight or branched chain alkyl group of 1-20 carbon atoms, typicallythose straight or branched chain alkyl groups such as methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutylgroup, sec-butyl group, tert-butyl group, n-pentyl group, isopentylgroup, sec-pentyl group, 1,1-dimethylpropyl group, n-hexyl group,n-heptyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group andn-octadecyl group.

The cycloalkyl group for R¹ may typically be the one of 3-8 carbon atomssuch as cyclopentyl group and cyclohexyl group. Typical alkenyl groupfor R¹ may be vinyl group, methallyl group, allyl group, etc. Typicalalkynyl group as R¹ may be ethynyl group, 1-propynyl group, etc.

The aryl group for R¹ may typically be phenyl group, alkyl-substitutedphenyl group, such as o-tolyl group, m-tolyl group, p-tolyl group,2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group,3,4-xylyl group, 3,5-xylyl group, mesityl group, 1-naphthyl group, etc.The aralkyl group for R¹ may typically be a lower alkyl groupsubstituted with phenyl group, such as benzyl group, phenylethyl group(namely phenethyl group), etc.

The substituent R² is a secondary alkyl group, a tertiary alkyl group, acycloalkyl group or an aryl group. The secondary alkyl group for R² maythe one of 3-10 carbon atoms and typically isopropyl group, sec-butylgroup, sec-pentyl group, etc.

The tertiary alkyl group R² may be those of 4-10 carbon atoms andtypically tert-butyl group, 1,1-dimethylpropyl group,1-ethyl-1-methylpropyl group, 1,1,2-trimethylpropyl group and1,1-diethylpropyl group.

The cycloalkyl group for R² may be those of 3-8 carbon atoms such ascyclopentyl group and cyclohexyl group. The aryl group for R² may bethose of the same range as exemplified for the group R¹ above.

Preferred examples of the compound of the formula (IV) may includetetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane,vinyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,phenylmethyldichlorosilane, etc.

The alcohol R³OH of the formula (V) to be reacted with the compound ofthe formula (IV) is a primary or secondary alkylalcohol or acycloalkylalcohol or an aralkyl alcohol.

Of the alcohol of the formula (V) above, the alkylalcohol (alkanol) maytypically be methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol, etc. The cycloalkylalcohol may typically becyclopentylalcohol and cyclohexylalcohol. Typical aralkylalcohol may bebenzylalcohol, phenylethylalcohol, etc.

The step for the alkoxylation or aralkyloxylation reaction, where thetetrachlorosilane or organochlorosilane of the general formula (IV) isreacted with the alcohol of the formula (V), is preferably effected byusing 0.5-2 moles, particularly 0.5-1.5 moles of the alcohol of theformula (V) for the reaction with 1 mole of the tetrachlorosilane ororganochlorosilane of the formula (IV). The step for the alkoxylation oraralkyloxylation reaction may be conducted either in the absence of asolvent or in an aprotic organic solvent. As such aprotic organicsolvent, there may be used an ether-type solvent such as diethylether,tetrahydrofuran and the like which is conventionally used in Grignardreactions, or a hydrocarbon-type solvent such as hexane, toluene and thelike. These solvents may be used alone or in any combination of two ormore of them. The reaction step for the alkoxylation or aralkyloxylationmay be carried out at a temperature in the range of −10° C.-150° C.,preferably 0° C.-100° C. The reaction with the alcohol of the formula(V) will generates hydrogen chloride gas as a by-product, and it isnecessary to expel the gas from the reaction system.

After the completion of the alkoxylation or aralkyloxylation reactionabove, there is obtained a reaction solution containing a mono(alkoxy,cycloalkyloxy or aralkyloxy)-chlorosilane of the general formula (I)thus produced. The compound of the general formula (I) can be recoveredby subjecting the reaction solution to a fractional distillation underatmospheric or a reduced pressure. Otherwise, said reaction solution maybe used as such for the first aspect process of this invention whichcorresponds to the subsequent Grignard reaction step.

Method (ii): Among the organo-unsubstituted or mono ordi-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)-tri, di ormonochlorosilanes of the general formula (I) to be used as the startingcompound, the organo-unsubstituted or mono or di-organo-monoalkoxy-tri,di or monochlorosilane of the general formula (I′)

wherein R¹, R² and R⁴ have the same meanings as defined above and x andy are the integers as defined above can be prepared by a methodcomprising reacting tetrachlorosilane or a di or mono-organo-di ortrichlorosilane of the general formula (IV)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (IV)wherein R¹ and R² have the same meanings as defined above and x and yare the integers as defined above, with an alkylene oxide or aglycidylether of the general formula (VI)

wherein R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms orR⁴ stands for an alkoxymethylene group, an alkenyloxymethylene group oraryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group.

The compound of the general formula (VI), where R⁴ is a hydrogen atom oran alkyl group, is an alkylene oxide of the general formula (VI) whichis an epoxy compound having the epoxy group at the end of thehydrocarbon chain, such as ethylene oxide, propylene oxide, etc.

On the other hand, the compound of the general formula (VI), where R⁴ isan alkoxymethylene group or an alkenyloxymethylene group or anaryloxymethylene group of the formula (A), is the compound of thegeneral formula (VI) which is a glycidylether. It may, for example, bebutylglycidyl ether, glycidylmethylether, etc.

Other examples of the glycidylether of the general formula (VI) mayinclude 2-ethylhexylglycidylether, octadecylglycidylether;allylglycidylether; glycidylphenylether.

The intended reaction in the Method (ii) may proceed by reacting 0.5-2moles of an alkylene oxide or a glycidylether of the general formula(VI) with 1 mole of tetrachlorosilane or the organo-chlorosilane of thegeneral formula (IV) in the absence of a solvent or in an aproticorganic solvent, for example in diethylether, at a temperature of −10°C.-150° C. A mixed solvent of hydrocarbons may also be used. The epoxygroup of the compound of the general formula (VI), when it is reactedwith the organo-chlorosilane of the general formula (IV), can undergothe ring-opening, thereby to incorporate therein the chloro group of thechlorosilane compound of the general formula (IV), and thus there isgenerated no hydrogen chloride gas, in contrast to Method (i) above.

Method (iii): The organo-unsubstituted or mono or di-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)-tri, di or monochlorosilane of the generalformula (I) where the group —OR³ of the formula (I) does not mean the2-substituted or unsubstituted-2-chloroethoxy group, which is to be usedas the starting compound, may also be prepared by a method comprisingmixing an alkoxysilane of the general formula (VII)(R¹)_(x)(R²)_(y)(OR³)_(z)Cl_(4−(x+y+z))  (VII)wherein R¹, R² and R³ have the same meanings as defined above, x standsfor an integer of 0 or 1, and y stands for an integer of 0, 1 or 2,provided that the integers for x and y are within the range of0≦(x+y)≦2; and z stands for an integer of 2, 3 or 4, provided that it iswithin the range of 2≦(x+y+z)≦4, with tetrachlorosilane or a di ormono-organo-di or trichlorosilane of the general formula (IV)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (IV)wherein R¹ and R² have the same meanings as defined above and x and yare the integers as defined above, and effecting a disproportionationreaction between the tetrachlorosilane or silane of the general formula(IV) and the alkoxysilane of the general formula (VII).

R¹ and R² of the alkoxysilane of the general formula (VII) stand for thesame substituents as R¹ and R² of the general formulae (I) or (IV).Concrete examples of the alkoxysilane of the general formula (VII) maybe tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane, phenylmethyldimethoxysilane, andphenylmethyldiethoxysilane, etc.

In the disproportionation reaction above, tetrachlorosilane or achlorosilane of the general formula (IV) and the alkoxysilane of thegeneral formula (VII) are preferably reacted in their proportions suchthat 0.1-3 moles, particularly 0.2-1.5 moles of an alkoxysilane of thegeneral formula (VII) are used for 1 mole of tetrachlorosilane or achlorosilane of the general formula (IV) so as to induce a highestproportion of a monochlorosilane of the general formula (I) to beproduced. The disproportionation reaction may be conducted in theabsence of a solvent at 0-50° C., preferably 10-30° C.

The reaction solution resulting from the step of the disproportionationreaction is a reaction solution of a mixture containing as a mainconstituent therein the organo-unsubstituted or mono ordi-organo-mono(alkoxy or cycloalkyloxy or aralkyloxy)chlorosilane of thegeneral formula (I), that is, the intended product of this reactionstep, and further containing the unreacted starting materials andby-products in which two or more chloro groups have been alkoxylated.

For the process of the first aspect of this invention which correspondsto the Grignard reaction step subsequent to said disproportionationstep, it is possible that the reaction solution as obtained from saiddisproportionation reaction may be used as such. However, the saidreaction solution may be once subjected to a fractional distillation toisolate a purified product of the mono-(alkoxy or cyclo-alkyloxy oraralkyloxy)silane of the general formula (I), which is then used in theprocess of the first aspect invention.

As is clear from the above explanation, the process of the first aspectof this invention is carried out by reacting a chlorosilane compound ofthe general formula (I) with a Grignard reagent of the general formula(II).

In the organometallic compound which is the Grignard reagent of thegeneral formula (II), the bulky hydrocarbon group R contained therein iseither a secondary alkyl group, a tertiary alkyl group or a cycloalkylgroup, or the hydrocarbon group R may be an aromatic hydrocarbon grouphaving an alkyl substituent as defined hereinbefore. Examples of saidsecondary alkyl group include isopropyl group, sec-butyl group andsec-pentyl group. Examples of said tertiary alkyl group includetert-butyl group, 1,1-dimethylpropyl group, 1-methyl-1-ethylpropylgroup, 1,1-diethylpropyl group and 1,1,2-trimethylpropyl group. As thesaid cycloalkyl group, there are listed cyclopentyl group, cyclohexylgroup, 1-methylcyclopentyl group, 1-methylcyclohexyl group and1-ethylcyclohexyl group.

For the aromatic hydrocarbon group having alkyl substituent, there areexemplified an alkyl-substituted phenyl group such as o-tolyl group,2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group andmesityl group, and 1-naphtyl group and the like. X stands for a halogenatom which is chlorine, bromine or iodine.

As concrete examples of the Grignard reagent of the general formula(II), there may be given isopropyl magnesium chloride, isopropylmagnesium bromide, isopropyl magnesium iodide; sec-butyl magnesiumchloride, sec-butyl magnesium bromide, sec-butyl magnesium iodide;sec-pentyl magnesium chloride, sec-pentyl magnesium bromide, sec-pentylmagnesium iodide; cyclopentyl magnesium chloride, cyclopentyl magnesiumbromide, cyclopentyl magnesium iodide; cyclohexyl magnesium chloride,cyclohexyl magnesium bromide, cyclohexyl magnesium iodide; tert-butylmagnesium chloride, tert-butyl magnesium bromide, tert-butyl magnesiumiodide; 1,1-dimethylpropyl magnesium chloride, 1,1-dimethylpropylmagnesium bromide, 1,1-dimethylpropyl magnesium iodide;1-methyl-1-ethylpropyl magnesium chloride, 1-methyl-1-ethylpropylmagnesium bromide, 1-methyl-1-ethylpropyl magnesium iodide;1,1-diethylpropyl magnesium chloride, 1,1-diethylpropyl magnesiumbromide, 1,1-diethylpropyl magnesium iodide; 1,1,2-trimethylpropylmagnesium chloride, 1,1,2-trimethylpropyl magnesium bromide,1,1,2-trimethylpropyl magnesium iodide; 1-methylcyclopentyl magnesiumchloride, 1-methylcyclopentyl magnesium bromide, 1-methylcyclopentylmagnesium iodide; 1-methylcyclohexyl magnesium chloride,1-methylcyclohexyl magnesium bromide, 1-methylcyclohexyl magnesiumiodide; 1-ethylcyclohexyl magnesium chloride, 1-ethylcyclohexylmagnesium bromide, 1-ethylcyclohexyl magnesium iodide; o-tolyl magnesiumchloride, o-tolyl magnesium bromide, o-tolyl magnesium iodide; 2,3-xylylmagnesium chloride, 2,3-xylyl magnesium bromide, 2,3-xylyl magnesiumiodide; 2,4-xylyl magnesium chloride, 2,4-xylyl magnesium bromide,2,4-xylyl magnesium iodide; 2,5-xylyl magnesium chloride, 2,5-xylylmagnesium bromide, 2,5-xylyl magnesium iodide; 2,6-xylyl magnesiumchloride, 2,6-xylyl magnesium bromide, 2,6-xylyl magnesium iodide;mesityl magnesium chloride, mesityl magnesium bromide, mesityl magnesiumiodide; 1-naphthyl magnesium chloride, 1-naphthyl magnesium bromide or1-naphthyl magnesium iodide, but these examples never limit the usableGrignard reagent thereto.

The Grignard reaction in the process according to the first aspect ofthis invention may be carried out in an ether-type solvent or in a mixedsolvent of an ether-type solvent with an aprotic organic solvent asabove-mentioned. As such aprotic organic solvent, there may beexemplified hydrocarbon-type solvent such as hexane, heptane, toluene,xylene, etc. The Grignard reagent of the general formula (II) maypreferably be used for the Grignard reaction in a proportion of 1-10moles, preferably 1-5 moles per 1 mole of the mono(alkoxy orcycloalkyloxy or aralkyloxy)chlorosilane of the general formula (I).

In case when the reaction solution resulting from the reaction step forthe preparation of the starting compound of the general formula (I) isto be used as such for the Grignard reaction, and when a reactionsolvent is used, it is usually desirable that the Grignard reaction iseffected in the same ether-type solvent or same mixed solvent of theether-type solvent with aprotic organic solvent as the reaction solventwhich was used in the preceding step. The Grignard reaction maypreferably be conducted at a temperature in the range of −10° C.-150°C., preferably of 20° C.-150° C. It is furthermore desirable that theGrignard reaction is carried out under an inert gas atmosphere such asnitrogen, argon, or the like, because the presence of oxygen in thereaction system brings about a reaction with the Grignard reagent, thusresulting in lowering of the yield of the desired reaction product.

The Grignard reaction may be conducted in a usual manner for 1-24 hoursuntil completion of the reaction. Subsequently, an appropriate amount ofa saturated aqueous ammonium chloride solution or a dilute sulfuric acidis added and mixed in the resulting reaction solution. Thus, theinorganic magnesium salt as deposited in the reaction solution can bedissolved in said aqueous ammonium chloride solution or dilute sulfuricacid. The organic layer is then separated from the aqueous layer, andthe organic layer so separated is subjected to a fractional distillation(namely, rectification) under atmospheric or reduced pressure, wherebythere can be recovered a fraction consisting of the desiredtri-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)silane of thegeneral formula (III).

In case when an organo-unsubstituted or mono(alkoxy, cycloalkyloxy oraralkyloxy)-trichlorosilane is used as the starting compound of thegeneral formula (I) and is reacted a Grignard reagent having a highlybulky tertiary alkyl group such as tert-butyl group, there is apossibility that the yield of the desiredtri-organo-substituted-mono(alkoxy, cycloalkyloxy or aralkyloxy)silaneso produced might be only very low, even if the Grignard reaction isconducted for a long period of time.

The tri-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)silane of thegeneral formula (III) can also be represented by the general formula(III′)

wherein R¹, R², R³, R, x and y each have the same meanings as definedabove.

As concrete examples of the mono(alkoxy, cycloalkyloxy oraralkyloxy)silane derivatives of the general formula (III) as producedby the process of the first aspect of this invention, there areenumerated triisopropylmethoxysilane, triispopropylethoxysilane,triisopropylisopropoxysilane, triisopropyl-n-butoxysilane,triisopropyl-2-chloroethoxysilane, triisopropylbenzyloxysilane,tri-sec-butylmethoxysilane, tri-sec-butylethoxysilane,tri-sec-butylisopropoxysilane, tri-sec-butyl-n-butoxysilane,tri-sec-butyl-2-chloroethoxysilane, tri-sec-butylbenzyloxysilane,tricyclohexylmethoxysilane, tricyclohexylethoxysilane,tricyclohexylisopropoxysilane, tricyclohexyl-n-butoxysilane,tricyclohexyl-2-chloroethoxysilane, tricyclohexylbenzyloxysilane,tri-o-tolylmethoxysilane, tri-o-tolylethoxysilane,tri-o-tolylisopropoxysilane, tri-o-tolyl-n-butoxysilane,tri-o-tolyl-2-chloroethoxysilane, tri-o-tolylbenzyloxysilane,diisopropylmethylmethoxysilane, diisopropylmethylethoxysilane,diisopropylmethyl-isopropoxysilane, diisopropylmethyl-n-butoxysilane,diisopropylmethyl-2-chloroethoxysilane,diisopropylmethylbenzyloxysilane, diisopropylvinylmethoxysilane,diisopropylvinylethoxysilane, diisopropylvinylisopropoxy-silane,diisopropylvinyl-n-butoxysilane, diisopropylvinyl-2-chloroethoxysilane,diisopropylvinylbenzyloxysilane, diisopropylphenylmethoxysilane,diisopropylphenylethoxysilane, diisopropylphenylisopropoxysilane,diisopropylphenyl-n-butoxysilane,diisopropylphenyl-2-chloroethoxysilane,diisopropylphenylbenzyloxysilane, di-sec-butylmethylmethoxysilane,di-sec-butylmethylethoxysilane, di-sec-butylmethylisopropoxysilane,di-sec-butylmethyl-n-butoxysilane,di-sec-butylmethyl-2-chloroethoxysilane,di-sec-butylmethylbenzyloxysilane, di-sec-butylvinylmethoxysilane,di-sec-butylvinylethoxysilane, di-sec-butylvinylisopropoxysilane,di-sec-butylvinyl-n-butoxysilane,di-sec-butylvinyl-2-chloroethoxysilane,di-sec-butylvinylbenzyloxysilane, di-sec-butylphenylmethoxysilane,di-sec-butylphenylethoxysilane, di-sec-butylphenylisopropoxysilane,di-sec-butylphenyl-n-butoxysilane,di-sec-butylphenyl-2-chloroethoxysilane,di-sec-butylphenylbenzyloxysilane, dicyclohexylmethylmethoxysilane,dicyclohexylmethylethoxysilane, dicyclohexylmethylisopropoxysilane,dicyclohexylmethyl-n-butoxysilane,dicyclohexylmethyl-2-chloroethoxysilane,dicyclohexylmethylbenzyloxysilane, dicyclohexylvinylmethoxysilane,dicyclohexylvinylethoxysilane, dicyclohexylvinylisopropoxysilane,dicyclohexylvinyl-n-butoxysilane,dicyclohexylvinyl-2-chloroethoxysilane,dicyclohexylvinylbenzyloxysilane, dicyclohexylphenylmethoxysilane,dicyclohexylphenylethoxysilane, dicyclohexylphenylisopropoxysilane,dicyclohexylphenyl-n-butoxysilane,dicyclohexylphenyl-2-chloroethoxysilane,dicyclohexylphenylbenzyloxysilane, di-o-tolylmethylmethoxysilane,di-o-tolylmethylethoxysilane, di-o-tolylmethylisopropoxysilane,di-o-tolylmethyl-n-butoxysilane, di-o-tolylmethyl-2-chloroethoxysilane,di-o-tolylmethylbenzyloxysilane, di-o-tolylvinylmethoxysilane,di-o-tolylvinylethoxysilane, di-o-tolylvinylisopropoxysilane,di-o-tolylvinyl-n-butoxysilane, di-o-tolylvinyl-2-chloroethoxysilane,di-o-tolylvinylbenzyloxysilane, di-o-tolylphenylmethoxysilane,di-o-tolylphenylethoxysilane, di-o-tolylphenylisopropoxysilane,di-o-tolylphenyl-n-butoxysilane, di-o-tolylphenyl-2-chloroethoxysilane,di-o-tolylphenylbenzyloxysilane, isopropyldiphenylmethoxysilane,isopropyldiphenylethoxysilane, isopropyldiphenylisopropoxysilane,isopropyldiphenyl-n-butoxysilane,isopropyldiphenyl-2-chloroethoxysilane,isopropyldiphenylbenzyloxysilane, sec-butyldiphenylmethoxysilane,sec-butyldiphenylethoxysilane, sec-butyldiphenylisopropoxysilane,sec-butyldiphenyl-n-butoxysilane,sec-butyldiphenyl-2-chloroethoxysilane,sec-butyldiphenylbenzyloxysilane, cyclohexyldiphenylmethoxysilane,cyclohexyldiphenylethoxysilane, cyclohexyldiphenylisopropoxysilane,cyclohexyldiphenyl-n-butoxysilane,cyclohexyldiphenyl-2-chloroethoxysilane,cyclohexyldiphenylbenzyloxysilane, o-tolyldiphenylmethoxysilane,o-tolyldiphenylethoxysilane, o-tolyldiphenylisopropoxysilane,o-tolyldiphenyl-n-butoxysilane, o-tolyldiphenyl-2-chloroethoxysilane,o-tolyldiphenylbenzyloxysilane, tert-butyldiphenylmethoxysilane,tert-butyldiphenylethoxysilane, tert-butyldiphenylisopropoxysilane,tert-butyldiphenyl-n-butoxysilane,tert-butyldiphenyl-2-chloroethoxysilane,tert-butyldiphenylbenzyloxysilane, tert-butylphenylmethylmethoxysilane,tertbutylphenyl-methylethoxysilane, tert-butylphenylmethylisopropoxysilane,tert-butylphenylmethyl-n-butoxysilane,tert-butylphenylmethyl-2-chloroethoxysilane, and the like, but theylimit by no means limit the scope of the silane derivatives of theformula (III) thereto.

Among the silane derivatives of the formula (III) which can be producedby the process of the first aspect of this invention,tri-isopropyl-monoalkoxysilane, tri-sec-butyl-monoalkoxysilane andtri-cyclohexyl-monoalkoxysilane are particularly useful as materials forthe synthesis of tri-organo-chlorosilanes which are a silylating agentto be used for protecting functional hydroxyl groups of chemicalintermediate compounds as produced in the various processes for thesynthetic production of medicines, and others; and also they are usefulfor the other useful applications.

As is clear from the above explanations, the step of preparing amono(methoxy, ethoxy, isopropoxy, n-butoxy or benzyloxy or2-chloroethoxy)-trichlorosilane of the formula (I) with starting from arelatively inexpensive tetrachlorosilane SiCl₄ can be carried out byreacting the tetrachlorosilane with 1 molar proportion of, for example,methanol, ethanol, n-butanol, isopropanol or benzyl alcohol or ethyleneoxide, etc., in the absence of a solvent or in an ether-type organicsolvent conventionally used for Grignard reactions (the organic solventmay be a mixed solvent comprising an ether and an aprotic aromatichydrocarbon solvent such as toluene).

The subsequent step of producing a desired tri-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)silane of the formula (III) having three ofthe secondary alkyl groups, cycloalkyl groups or the alkyl-substitutedaromatic hydrocarbon groups as defined above can next be carried out ina way such that the mono-(organo-oxy)-trichlorosilane compound of theformula (I) as produced in the above step or the reaction solutioncontaining said mono-(organo-oxy)-trichlorosilane compound of theformula (I) is reacted with a Grignard reagent of the formula (II) whichis containing a secondary alkyl group or a cycloalkyl group oralkyl-substituted aromatic hydrocarbon group. Moreover, it isadvantageous that said mono(alkoxy or cycloalkoxy oraralkyloxy)-trichlorosilane compound of the formula (I) so produced inthe preceding step as an intermediate product can directly be used forthe subsequent step even without making isolation of it from thereaction solution obtained in the preceding step, and that it is thuspossible to conduct the above-mentioned preceding step and thesubsequent step in a successive or consecutive manner.

According to a second aspect of this invention, therefore, there isprovided a process for the production of a tri-organo-mono(alkoxy,cycloalkyloxy or aralkyloxy)silane of the general formula (IIIa)(R^(a))₃—Si—(OR^(3a))  (IIIa)wherein R^(3a) stands for a straight or branched chain alkyl group of1-6 carbon atoms or a cycloalkyl group or an aralkyl group and R^(a)stands for a secondary alkyl group or a cycloalkyl group or analkyl-substituted aromatic hydrocarbon group as defined below, or forthe production of a tri-organo-mono-(2-substituted orunsubstituted-2-chloroethoxy)silane of the general formula (IIIb)

wherein R^(4a) stands for a hydrogen atom or an alkyl group of 1-8carbon atoms, or R^(4a) stands for a (C₁-C₂₀)alkyloxy-methylene group, a(C₂-C₁₀)alkenyloxymethylene group or an aryloxymethylene group, andR^(a) is as defined above and stands for a secondary alkyl group or acycloalkyl group, or R^(a) is an alkyl-substituted aromatic hydrocarbongroup as defined below, characterized in that the process comprises afirst step of reacting tetrachlorosilane with an alcohol of the formula(Va)R^(3a)—OH  (Va)wherein R^(3a) has the same meaning as defined above, or with analkylene oxide or a glycidylether of the formula (VIa)

wherein R^(4a) has the same meaning as defined above, in the absence ofany solvent or in the presence of an ether-type solvent or an aromatichydrocarbon solvent usually usable for the Grignard reaction, thereby toproduce either a mono(alkoxy or cycloalkyloxy oraralkyloxy)-trichlorosilane of the formula (Ia)(R^(3a)O)—Si—Cl₃  (Ia)wherein R^(3a) has the same meaning as defined above, or amono(2-substituted or unsubstituted-2-chloroethoxy)-trichlorosilane ofthe formula (Ib)(R^(3b)O)—Si—Cl₃  (Ib)wherein the group R^(3b)O— stands for the 2-substituted orunsubstituted-2-chloroethoxy group of the formula (A′)

where R^(4a) has the same meaning as defined above; and a second step ofadmixing the reaction solution resulting from said first step andcontaining therein either the mono(alkoxy or cycloalkyloxy oraralkyloxy)-trichlorosilane of the formula (Ia) as produced or themono(2-substituted or unsubstituted-2-chloroethoxy)-trichlorosilane ofthe formula (Ib) as produced, with a Grignard reagent of the formula(II′)R^(a)MgX  (II′)wherein R^(a) stands for a secondary alkyl group or a cycloalkyl group,or R^(a) stands for an alkyl-substituted aromatic hydrocarbon group ofwhich the alkyl substituent is bonding to a carbon atom present in thearomatic hydrocarbon group, with said carbon atom being adjacent to thecarbon atom of the aromatic hydrocarbon group that is bonding to themagnesium atom, and X stands for a chlorine, bromine or iodine atom, andsubsequently effecting the intended Grignard reaction between thecompound of the formula (Ia) or (Ib) and the Grignard reagent of theformula (II′), to produce the silane compound of the formula (IIIa) or(IIIb).

In the process of the second aspect of this invention, the first stepthereof, which is effected for preparing the starting compound offormula (Ia) or (Ib) usable to be used for the first aspect process ofthis invention, may be carried out in the same manner as that of theaforesaid Method (i) or Method (ii), wherein tetrachlorosilane or anorgano-chlorosilane compound of the general formula (IV) is reacted withan alcohol R³OH of the general formula (V) or an alkylene oxide or aglycidylether of the general formula (VI). The second step of thissecond aspect process of this invention may be carried out in the samemanner as that explained for the first aspect process of this invention.

In accordance with the production processes of the first and secondaspects of this invention, there can be produced easily and efficientlya tri-organo-mono(alkoxy or cycloalkyloxy or aralkyloxy)silane compoundhaving at least two bulky hydrocarbon groups therein, without thenecessity of using a lithium reagent which is difficult to be handled,and also without the necessity of using the highly toxic catalysts.

Apart from our investigations about the first and second aspects of thisinvention, we now have also eagerly proceeded our investigations withthe intention of developing a novel process for the production of atri-organo-mono-chlorosilane. In the related prior art, there was acommon knowledge that when a tri-organo-silane compound having ahydrolyzable group is treated with hydrochloric acid added thereto, itis hydrolyzed to form a silanol which can then be dehydrated andcondensed to be converted into siloxane compounds.

Unexpectedly, however, we have now found, as a result of ourinvestigations now made, that a tri-organo-silane can be converted intoa tri-organo-chlorosilane if hydrochloric acid is reacted with thetri-organo-silane under an appropriate condition. Our third aspect ofthis invention has now been accomplished on the basis of on thisfinding.

Thus, according to a third aspect of this invention, there is provided aprocess for the production of a tri-organo-monochlorosilane of thegeneral formula (XIIa)(R¹)(R²)(R³)SiCl  (XIIa)wherein R¹, R² and R³ are the same as or different from each other andeach stand for a primary, secondary or tertiary alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl groupor an aryl group, but wherein R¹, R² and R³ each and all do notrepresent methyl group at the same time, or for the production of atri-organo-monochloro-silane of the general formula (XIIb)(R¹)(R²)(R^(3a))SiCl  (XIIb)wherein R¹ and R² have the same meanings as defined above and R^(3a) isa secondary alkyl group or a tertiary alkyl group or a cycloalkyl group,or R^(3a) is an alkyl-substituted aromatic hydrocarbon group of whichthe alkyl substituent is bonding to a carbon atom present in thearomatic hydrocarbon group, with said carbon atom being adjacent to thecarbon atom of the aromatic hydrocarbon group that is bondable to amagnesium atom, characterized in the process comprises reactinghydrochloric acid with a tri-organo-silane compound of the formula (XIa)(R¹)(R²)(R³)SiZ¹  (XIa)wherein R¹, R² and R³ each have the same meanings as defined above andZ¹ is a hydrolyzable group, or particularly a tri-organo-silane compoundcontaining the bulky hydrocarbon group R^(3a) therein and having theformula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb)wherein R¹, R² and R^(3a) have the same meanings as defined above and Z²is a primary or secondary alkyloxy group, a cycloalkyloxy group or anaralkyloxy group, or Z² is a 2-substituted orunsubstituted-2-chloroethoxy group of the formula (A)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, or R⁴is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group, thereby to produce atri-organo-monochlorosilane of the formula (XIIa) or atri-organo-monochlorosilane of the formula (XIIb).

It is to be noted that the definitions of R¹ and R² for the generalformula (XIa) or (XIb) according to the third aspect of this inventionare broader than those of R¹ and R² as given for the general formula (I)according to the first aspect process of this invention.

The hydrolyzable group Z¹ in the tri-organo-silane compounds of thegeneral formula (XIa) to be used in the process of the third aspect ofthis invention is an substituted or unsubstituted alkoxy group, acycloalkyloxy group, an aralkyloxy group, an acyloxy group, amino group,an inorganic acid ester residue, or a pseudohalogen group, particularlycyano group. Examples of the alkoxy group as the hydrolyzable group Z¹may include methoxy group, ethoxy group, n-propoxy group, isopropoxygroup, n-butoxy group, sec-butoxy group, isobutyloxy group, n-hexyloxygroup, cyclohexyloxy group, n-octyloxy group, 2-ethylhexyloxy group,3-methylbutoxy group, phenoxy group, 2-chloroethoxy group,2-chloro-3-n-butoxypropoxy group, etc., but they do not limit the scopeof the group Z¹ thereto.

As typical example of an acyloxy group for the hydrolyzable group Z¹,there is given acetoxy group, and as amino group, there are not onlysimple amino group, but also dimethylamino, diethylamino,di-n-propylamino, diisopropylamino, di-n-butylamino and di-n-octylaminogroups, etc. Example of the ester residue of an inorganic acid for Z¹ issulfuric acid ester residue, etc. As examples of pseudohalogen group forZ¹, there are cyano group, thiocyano group, isothiocyano group, etc.,but they do not limit the scope of such group. Moreover, thechlorination reaction of the process of the third aspect of thisinvention is particularly suitable for the preparation of atri-organo-monochlorosilane having a bulky hydrocarbon substituent andhaving the general formula (XIb).

The organo groups R¹, R² and R³ of the tri-organo-silane compound of thegeneral formula (XIa) to be used as the starting compound in the thirdaspect process of this invention may be equal to each other or aredifferent from each other, and they may be a primary, secondary ortertiary alkyl group, a cycloalkyl group, an alkenyl group, an alkynylgroup, or an aralkyl group or an aryl group.

The alkyl group for R¹, R² or R³ of the general formula (XIa) maypreferably be a straight or branched chain alkyl group of 1-20 carbonatoms and concretely may be methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, isobutyl group, sec-butyl group,tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group,1,1-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group,2-ethylhexyl group, n-dodecyl group, n-octadecyl group and others. In acase where the alkyl group as R¹, R², R³ is a secondary or tertiaryalkyl group, it may be a secondary or tertiary alkyl group as shownhereinafter for the group R^(3a). The cycloalkyl group for R¹, R² or R³in the general formula (XIa) may be that of 3-8 carbon atoms such ascyclopentyl group, cyclohexyl group, and others. As the alkenyl groupfor R¹, R² or R³ in the general formula (XIa), there may be listed vinylgroup, methallyl group, allyl group and others. As the alkynyl group forR¹, R² or R³, there may be listed ethynyl group, 1-propynyl group andothers. As the aryl group for R¹, R² or R³, there may be exemplifiedphenyl group, an alkyl-substituted phenyl group, such as o-tolyl group,m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group,2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group,mesityl group, or 1-naphthyl group, etc. As the aralkyl group for R¹, R²or R³, there may be mentioned a phenyl-substituted lower alkyl group,for example, benzyl group, phenylethyl group (namely, phenethyl group),and the like.

The organo group R¹ and R² in the tri-organo-silane compound of thegeneral formula (XIb) may be the same as those for R¹ and R² of thegeneral formula (XIa). The organo group R^(3a) of the compound of thegeneral formula (XIb) is a secondary alkyl group, a tertiary alkyl groupor a cycloalkyl group, or an alkyl-substituted aromatic hydrocarbongroup. The secondary alkyl group as R^(3a) is preferably that of 3-10carbon atoms, such as, for example, isopropyl group, sec-butyl group andsec-pentyl group. The tertiary alkyl group as R^(3a) is preferably thatof 4-10 carbon atoms, such as, for example, tert-butyl group,1,1-dimethylpropyl group, 1-methyl-1-ethylpropyl group, 1,1-diethylethylgroup, 1,1,2-tri-methylpropyl group and the like. The cycloalkyl groupas R^(3a) is preferably those of 3-8 carbon atoms, such as, for example,cyclopentyl group, cyclohexyl group, 1-methylcyclopentyl group,1-methylcyclohexyl group, 1-ethylcyclohexyl group, etc. Thealkyl-substituted aromatic hydrocarbon group for R^(3a) is preferablythat of 7-10 carbon atoms, such as an alkyl-substituted phenyl group,for example, o-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylylgroup, 2,6-xylyl group, mesityl group, or 1-naphthyl group, and others.

In the process of the third aspect of this invention, hydrochloric acidmay be used in a proportion of 1-50 moles of hydrogen chloride per 1mole of the starting tri-organo-silane compound of the general formula(XIa) or (XIb). The concentration of the hydrochloric acid depends uponthe hydrolyzability of the tri-organo-chlorosilane produced of thegeneral formula (XIIa) or (XIIb). The available range of theconcentration of hydrochloric acid may be from 10% (by weight) to thesaturated concentration (37% by weight), within which an appropriateconcentration of HCl can be chosen. In a case where the resultingtri-organo-monochlorosilane product of the general formula (XIIa) or(XIIb) is highly hydrolyzable, it is desirable to use a large amount ofhydrochloric acid having a high hydrogen chloride concentration. It isalso possible to use hydrochloric acid in combination with hydrogenchloride gas. The reaction temperature for the chlorination reaction maybe −20° C.-100° C., preferably −10° C.-50° C.

In the process of the third aspect of this invention, the reaction withhydrochloric acid may be carried out in an organic solvent. As theorganic solvent, there may be mentioned an alcohol solvent, such asmethanol, ethanol; or an aliphatic hydrocarbon solvent, such as hexane,heptane; or an aromatic hydrocarbon solvent, such as toluene, benzene,xylene; or an ether solvent, such as tetrahydrofuran, and the like. Theorganic solvent may be added to the reaction medium, either alone or incombination. In a case where an organic solvent is used, theconcentration of the organic solvent in the reaction medium is notparticularly limited. However, if a protic solvent such as alcohols isused, the concentration of the protic organic solvent is possible to belimited, depending on the hydrolyzability of the intended product.

As concrete examples of the tri-organo-silane compound of the generalformula (XIa) or (XIb) to be used as the starting compound for theprocess of the third aspect of this invention, there may be listed,first of all, triethylmethoxysilane, includingtriisopropylmethoxysilane, triisopropylethoxysilane,triisopropylisopropoxysilane, triisopropyl-n-butoxysilane,triisopropyl-2-chloroethoxysilane, triisopropyl-3-methylbutoxysilane,triisopropylbenzyloxysilane, tri-sec-butylmethoxysilane,tri-sec-butylethoxysilane, tri-sec-butylisopropoxysilane,tri-sec-butyl-n-butoxysilane, tri-sec-butyl-2-chloroethoxysilane,tri-sec-butyl-3-methylpentyloxysilane, tri-sec-butylbenzyloxysilane,tricyclohexylmethoxysilane, tricyclohexylethoxysilane,tricyclohexylisopropoxysilane, tricyclohexyl-n-butoxysilane,tricyclohexyl-2-chloroethoxysilane,tricyclohexyl-2-cyclohexylethoxysilane, tricyclohexylbenzyloxysilane,tri-o-tolylmethoxysilane, tri-o-tolylethoxysilane,tri-o-tolylisopropoxysilane, tri-o-tolyl-n-butoxysilane,tri-o-tolyl-2-chloroethoxysilane, tri-o-tolyl-2-o-tolylethoxysilane,tri-o-tolylbenzyloxysilane, diisopropylmethylmethoxysilane,diisopropylmethylethoxysilane, diisopropylmethylisopropoxysilane,diisopropylmethyl-n-butoxysilane,diisopropylmethyl-2-chloroethoxysilane,diisopropylmethyl-3-methylbutoxysilane,diisopropylmethylbenzyloxysilane, diisopropylvinylmethoxysilane,diisopropylvinylethoxysilane, diisopropylvinylisopropoxysilane,diisopropylvinyl-n-butoxysilane, diisopropylvinyl-2-chloroethoxysilane,diisopropylvinyl-3-methylbutoxysilane, diisopropylvinylbenzyloxysilane,diisopropylphenylmethoxysilane, diisopropylphenylethoxysilane,diisopropylphenylisopropoxysilane, diisopropylphenyl-n-butoxysilane,diisopropylphenyl-2-chloroethoxysilane,diisopropylphenyl-3-methylbutoxysilane,diisopropylphenylbenzyloxysilane, di-sec-butylmethylmethoxysilane,di-sec-butylmethylethoxysilane, di-sec-butylmethylisopropoxysilane,di-sec-butylmethyl-n-butoxysilane,di-sec-butylmethyl-2-chloroethoxysilane,di-sec-butylmethyl-3-methylpentyloxysilane,di-sec-butylmethylbenzyloxysilane, di-sec-butylvinylmethoxysilane,di-sec-butylvinylethoxysilane, di-sec-butylvinylisopropoxysilane,di-sec-butylvinyl-n-butoxysilane,di-sec-butylvinyl-2-chloroethoxysilane,di-sec-butylvinyl-3-methylpentyloxysilane,di-sec-butylvinylbenzyloxysilane, di-sec-butylphenylmethoxysilane,di-sec-butylphenylethoxysilane, di-sec-butylphenylisopropoxysilane,di-sec-butylphenyl-n-butoxysilane,di-sec-butylphenyl-2-chloroethoxysilane,di-sec-butylphenyl-3-methylpentyloxysilane,di-sec-butylphenylbenzyloxysilane, dicyclohexylmethylmethoxysilane,dicyclohexylmethylethoxysilane, dicyclohexylmethylisopropoxysilane,dicyclohexylmethyl-n-butoxysilane,dicyclohexylmethyl-2-chloroethoxysilane,dicyclohexylmethyl-2-cyclohexylethoxysilane,dicyclohexylmethylbenzyloxysilane, dicyclohexylvinylmethoxysilane,dicyclohexylvinylethoxysilane, dicyclohexylvinylisopropoxysilane,dicyclohexylvinyl-n-butoxysilane,dicyclohexylvinyl-2-chloroethoxysilane,dicyclohexylvinyl-2-cyclohexylethoxysilane,dicyclohexylvinylbenzyloxysilane, dicyclohexylphenylmethoxysilane,dicyclohexylphenylethoxysilane, dicyclohexylphenylisopropoxysilane,dicyclohexylphenyl-n-butoxysilane,dicyclohexylphenyl-2-chloroethoxysilane,dicyclohexylphenyl-2-cyclohexylethoxysilane,dicyclohexylphenylbenzyloxysilane, di-o-tolylmethylmethoxysilane,di-o-tolylmethylethoxysilane, di-o-tolylmethylisopropoxysilane,di-o-tolylmethyl-n-butoxysilane, di-o-tolylmethyl-2-chloroethoxysilane,di-o-tolylmethyl-2-o-tolylethoxysilane, di-o-tolylmethylbenzyloxysilane,di-o-tolylvinylmethoxysilane, di-o-tolylvinylethoxysilane,di-o-tolylvinylisopropoxysilane, di-o-tolylvinyl-n-butoxysilane,di-o-tolylvinyl-2-chloroethoxysilane,di-o-tolylvinyl-2-o-tolylethoxysilane, di-o-tolylvinylbenzyloxysilane,di-o-tolylphenylmethoxysilane, di-o-tolylphenylethoxysilane,di-o-tolylphenylisopropoxysilane, di-o-tolylphenyl-n-butoxysilane,di-o-tolylphenyl-2-chloroethoxysilane,di-o-tolylphenyl-2-o-tolylethoxysilane, di-o-tolylphenylbenzyloxysilane,isopropyldimethylmethoxysilane, isopropyldimethylethoxysilane,isopropyldimethylisopropoxysilane, isopropyldimethyl-n-butoxysilane,isopropyldimethyl-2-chloroethoxysilane, isopropyldimethyl-3-methylbutoxysilane, isopropyldimethylbenzyloxysilane,isopropyldivinylmethoxysilane, isoprpyldivinylethoxysilane,isopropyldivinylisopropoxysilane, isopropyldivinyl-n-butoxysilane,isopropyldivinyl-2-chloroethoxysilane,isopropyldivinyl-3-methylbutoxysilane, isopropyldivinylbenzyloxysilane,isopropyldiphenylmethoxysilane, isopropyldiphenylethoxysilane,isopropyldiphenylisopropoxysilane, isopropyldiphenyl-n-butoxysilane,isopropyldiphenyl-2-chloroethoxysilane,isopropyldiphenyl-3-methylbutoxysilane,isopropyldiphenylbenzyloxysilane, sec-butyldimethylmethoxysilane,sec-butyldimethylethoxysilane, sec-butyldimethylisopropoxysilane,sec-butyldimethyl-n-butoxysilane,sec-butyldimethyl-2-chloroethoxysilane,sec-butyldimethyl-3-methylpentyloxysilane,sec-butyldimethylbenzyloxysilane, sec-butyldivinylmethoxysilane,sec-butyldivinylethoxysilane, sec-butyldivinylisopropoxysilane,sec-butyldivinyl-n-butoxysilane, sec-butyldivinyl-2-chloroethoxysilane,sec-butyldivinyl-3-methylpentyloxysilane,sec-butyldivinylbenzyloxysilane, sec-butyldiphenylmethoxysilane,sec-butyldiphenylethoxysilane, sec-butyldiphenylisopropoxysilane,sec-butyldiphenyl-n-butoxysilane,sec-butyldiphenyl-2-chloroethoxysilane,sec-butyldiphenyl-3-methylpentyloxysilane,sec-butyldiphenylbenzyloxysilane, cyclohexyldimethylmethoxysilane,cyclohexyldimethylethoxysilane, cyclohexyldimethylisopropoxysilane,cyclohexyldimethyl-n-butoxysilane,cyclohexyldimethyl-2-chloroethoxysilane,cyclohexyldimethyl-2-cyclohexylethoxysilane,cyclohexyldimethylbenzyloxysilane, cyclohexyldivinylmethoxysilane,cyclohexyldivinylethoxysilane, cyclohexyldivinylisopropoxysilane,cyclohexyldivinyl-n-butoxysilane,cyclohexyldivinyl-2-chloroethoxysilane,cyclohexyldivinyl-2-cyclohexylethoxysilane,cyclohexyldivinylbenzyloxysilane, cyclohexyldiphenylmethoxysilane,cyclohexyldiphenylethoxysilane, cyclohexyldiphenylisopropoxysilane,cyclohexyldiphenyl-n-butoxysilane,cyclohexyldiphenyl-2-chloroethoxysilane,cyclohexyldiphenyl-2-cyclohexylethoxysilane,cyclohexyldiphenylbenzyloxysilane, o-tolyldimethylmethoxysilane,o-tolyldimethylethoxysilane, o-tolyldimethylisopropoxysilane,o-tolyldimethyl-n-butoxysilane, o-tolyldimethyl-2-chloroethoxysilane,o-tolyldimethyl-2-o-tolylethoxysilane, o-tolyldimethylbenzyloxysilane,o-tolyldivinylmethoxysilane, o-tolyldivinylethoxysilane,o-tolyldivinylisopropoxysilane, o-tolyldimethyl-n-butoxysilane,o-tolyldivinyl-2-chloroethoxysilane,o-tolyldivinyl-2-o-tolylethoxysilane, o-tolyldivinylbenzyloxysilane,o-tolyldiphenylmethoxysilane, o-tolyldiphenylethoxysilane,o-tolyldiphenylisopropoxysilane, o-tolyldiphenyl-n-butoxysilane,o-tolyldiphenyl-2-chloroethoxysilane,o-tolyldiphenyl-2-o-tolylethoxysilane, o-tolyldiphenylbenzyloxysilane,tert-butyldimethylmethoxysilane, tert-butyldimethylethoxysilane,tert-butyldimethylisopropoxysilane, tert-butyldimethyl-n-butoxysilane,tert-butyldimethyl-2-chloroethoxysilane,tert-butyldimethyl-3,3-dimethylbutoxysilane, tert-butyldimethylbenzyloxysilane, tert-butyldivinylmethoxysilane, tert-butyldivinylethoxysilane,tert-butyldivinylisopropoxysilane, tert-butyldivinyl-n-butoxysilane,tert-butyldivinyl-2-chloroethoxysilane,tert-butyldivinyl-3,3-dimethylbutoxysilane,tert-butyldivinylbenzyloxysilane, tert-butyldiphenylmethoxysilane,tert-butyldiphenylethoxysilane, tert-butyldiphenylisopropoxysilane,tert-butyldiphenyl-n-butoxysilane,tert-butyldiphenyl-2-chloroethoxysilane,tert-butyldiphenyl-3,3-dimethylbutoxysilane,tert-butyldiphenylbenzyloxysilane, tert-butylvinylmethylmethoxysilane,tert-butylvinylmethylethoxysilane,tert-butylvinylmethylisopropoxysilane,tert-butylvinylmethyl-n-butoxysilane,tert-butylvinylmethyl-2-chloroethoxysilane,tert-butylvinylmethyl-3,3-dimethyl-n-butoxysilane,tert-butylphenylmethylmethoxysilane, tert-butylphenylmethylethoxysilane,tert-butylphenylmethylisopropoxysilane,tert-butylphenylmethyl-n-butoxysilane,tert-butylphenylmethyl-2-chloroethoxysilane,tert-butylphenylmethyl-3,3-dimethylbutoxysilane, and others.

The unsubstituted or substituted alkoxy groups above-exemplified, suchas methoxy group, ethoxy group, isopropoxy group, 2-chloroethoxy group,butoxy group, present in the silane compound of the general formula(XIa) or (XIb) can be replaced by a chloro group by the treatment withhydrochloric acid in the process of the third aspect of this inventionto give the corresponding tri-organo-monochlorosilane.

As concrete examples of the tri-organo-monochlorosilanes produced by thethird aspect process of this invention, there may be listedtriethylchlorosilane, tri-n-propylchlorosilane,triisopropylchlorosilane, tri-n-butylchlorosilane,triisobutylchlorosilane, tri-sec-butylchlorosilane,tri-tert-butylchlorosilane, tri-n-octylchlorosilane,tricyclopentylchlorosilane, tricyclohexylchlorosilane,trimethallylchlorosilane, tri-o-tolylchlorosilane,tri-2,3-xylylchlorosilane, tri-2,4-xylylchlorosilane,tri-2,5-xylylchlorosilane, tri-2,6-xylylchlorosilane,tri-3,4-xylylchlorosilane, tri-3,5-xylylchlorosilane,trimesitylchlorosilane, methyldi-n-propylchlorosilane,methyldiisopropylchlorosilane, methyldi-n-butylchlorosilane,methyldiisobutylchlorosilane, methyldi-sec-butylchlorosilane,methyldi-tert-butylchlorosilane, methyldi-n-octylchlorosilane,methyldicyclopentylchlorosilane, methyldicyclohexylchlorosilane,methyldimethallylchlorosilane, methyldi-o-tolylchlorosilane,methyldi-2,3-xylylchlorosilane, methyldi-2,4-xylylchlorosilane,methyldi-2,5-xylylchlorosilane, methyldi-2,6-xylylchlorosilane,methyldi-3,4-xylylchlorosilane, methyldi-3,5-xylylchlorosilane,methyldimesitylchlorosilane, vinyldiethylchlorosilane,vinyldi-n-propylchlorosilane, vinyldiisopropylchlorosilane,vinyldi-n-butylchlorosilane, vinyldiisobutylchlorosilane,vinyldi-sec-butylchlorosilane, vinyldi-tert-butylchlorosilane,vinyldi-n-octylchlorosilane, vinyldicyclopentylchlorosilane,vinyldicyclohexylchlorosilane, vinyldimethallylchlorosilane,vinyldi-o-tolylchlorosilane, vinyldi-2,3-xylylchlorosilane,vinyldi-2,4-xylylchlorosilane, vinyldi-2,5-xylylchlorosilane,vinyldi-2,6-xylylchlorosilane, vinyldi-3,4-xylylchlorosilane,vinyldi-3,5-xylylchlorosilane, vinyldimesitylchlorosilane,phenyldiethylchlorosilane, phenyldi-n-propylchlorosilane,phenyldiisopropylchlorosilane, phenyldi-n-butylchlorosilane,phenyldiisobutylchlorosilane, phenyldi-sec-butylchlorosilane,phenyldi-tert-butylchlorosilane, phenyldi-n-octylchlorosilane,phenyldicyclopentylchlorosilane, phenyldicyclohexylchlorosilane,phenyldimethallylchlorosilane, phenyldi-o-tolylchlorosilane,phenyldi-2,3-xylylchlorosilane, phenyldi-2,4-xylylchlorosilane,phenyldi-2,5-xylylchlorosilane, phenyldi-2,6-xylylchlorosilane,phenyldi-3,4-xylylchlorosilane, phenyldi-3,5-xylylchlorosilane,phenyldimesitylchlorosilane, n-propyldimethylchlorosilane,isopropyldimethylchlorosilane, n-butyldimethylchlorosilane,isobutyldimethylchlorosilane, sec-butyldimethylchlorosilane,tert-butyldimethylchlorosilane, n-octyldimethylchlorosilane,cyclopentyldimethylchlorosilane, cyclohexyldimethylchlorosilane,methallyldimethylchlorosilane, o-tolyldimethlychlorosilane,2,3-xylyldimethylchlorosilane, 2,4-xylyldimethylchlorosilane,2,5-xylyldimethylchlorosilane, 2,6-xylyldimethylchlorosilane,3,4-xylyldimethylchlorosilane, 3,5-xylyldimethylchlorosilane,mesityldimethylchlorosilane, n-propylvinylmethylchlorosilane,isopropylvinylmethylchlorosilane, n-butylvinylmethylchlorosilane,isobutylvinylmethylchlorosilane, sec-butylvinylmethylchlorosilane,tert-butylvinylmethylchlorosilane, n-octylvinylmethylchlorosilane,cyclopentylvinylmethylchlorosilane, cyclohexylvinylmethylchlorosilane,methallylvinylmethylchlorosilane, o-tolylvinylmethylchlorosilane,2,3-xylylvinylmethylchlorosilane, 2,4-xylylvinylmethylchlorosilane,2,5-xylylvinylmethylchlorosilane, 2,6-xylylvinylmethylchlorosilane,3,4-xylylvinylmethylchlorosilane, 3,5-xylylvinylmethylchlorosilane,mesitylvinylmethylchlorosilane, n-propylphenylmethylchlorosilane,isopropylphenylmethylchlorosilane, n-butylphenylmethylchlorosilane,isobutylphenylmethylchlorosilane, sec-butylphenylmethylchlorosilane,tert-butylphenylmethylchlorosilane, n-octylphenylmethylchlorosilane,cyclopentylphenylmethylchlorosilane, cyclohexylphenylmethylchlorosilane,methallylphenylmethylchlorosilane, o-tolylphenylmethylchlorosilane,2,3-xylylphenylmethylchlorosilane, 2,4-xylylphenylmethylchlorosilane,2,5-xylylphenylmethylchlorosilane, 2,6-xylylphenylmethylchlorosilane,3,4-xylylphenylmethylchlorosilane, 3,5-xylylphenylmethylchlorosilane,mesitylphenylmethylchlorosilane, n-propyldivinylchlorosilane,isopropyldivinylchlorosilane, n-butyldivinylchlorosilane,isobutyldivinylchlorosilane, sec-butyldivinylchlorosilane,tert-butyldivinyl chlorosilane, n-octyldivinylchlorosilane,cyclopentyldivinylchlorosilane, cyclohexyldivinylchlorosilane,methallyldivinylchlorosilane, o-tolyldivinylchlorosilane,2,3-xylyldivinylchlorosilane, 2,4-xylyldivinylchlorosilane,2,5-xylyldivinylchlorosilane, 2,6-xylyldivinylchlorosilane,3,4-xylyldivinylchlorosilane, 3,5-xylyldivinylchlorosilane,mesityldivinylchlorosilane, n-propyldiphenylchlorosilane,isopropyldiphenylchlorosilane, n-butyldiphenylchlorosilane,isobutyldiphenylchlorosilane, sec-butyldiphenylchlorosilane,tert-butyldiphenylchlorosilane, n-octyldiphenylchlorosilane,cyclopentyldiphenylchlorosilane, cyclohexyldiphenylchlorosilane,methallyldiphenylchlorosilane, o-tolyldiphenylchlorosilane,2,3-xylyldiphenylchlorosilane, 2,4-xylyldiphenylchlorosilane,2,5-xylyldiphenylchlorosilane, 2,6-xylyldiphenylchlorosilane,3,4-xylyldiphenylchlorosilane, 3,5-xylyldiphenylchlorosilane,mesityldiphenylchlorosilane, etc., but these particular examples do notlimit the scope of the intended tri-organo-monochlorosilane.

Among the compound exemplified above which may be produced by the thirdaspect process of this invention, triisopropylchlorosilane,tri-sec-butylchlorosilane, tricyclopentylchlorosilane,tricyclohexylchlorosilane and tertbutyldimethylchlorosilane areparticularly useful for the purpose of the production of medicines andothers and are also useful as a tri-organo-chlorosilane which is asilylating agent to be used for protecting the functional groups ofsynthetic intermediates or is an intermediate for preparation of suchsilylating agent.

Several methods may be used for the preparation of a tri-organo-silanecompound of the general formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb)which contains a bulky hydrocarbon group R^(3a) such as a secondary ortertiary alkyl group, and which is used as a starting compound in thethird aspect process of this invention.

To be concrete, there are available Method (A), Method (B), Method (C),Method (D), Method (E) and Method (F) as described in (i)-(vi) below.

-   (i) Method (A) is adapted for the preparation of a tri-organo-silane    compound of the general formula (XIb)    (R¹)(R²)(R^(3a))SiZ²  (XIb)    where the group Z² in the general formula (XIb) does not mean the    2-substituted or unsubstituted-2-chloroethoxy group of the formula    (A), which is to be used as the starting compound. This Method (A)    comprises reacting tetrachlorosilane or a di or mono-organo-di or    trichlorosilane of the general formula (XIII)    (R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XIII)    wherein R¹ and R² have the same meanings as defined above and x and    y each are an integer of 0, 1 or 2, and are to be within the range    of 0≦(x+y)≦2, with an alcohol of the general formula (XIV)    R⁶OH  (XIV)    wherein R⁶ stands for a primary or secondary alkyl group, a    cycloalkyl group or an aralkyl group, thereby to produce an    organo-unsubstituted or mono-organo or di-organo-mono(alkoxy,    cycloalkyloxy or aralkyloxy)-tri, di or monochlorosilane of the    general formula (XVa)    (R¹)_(x)(R²)_(y)SiCl_(3−(x+y))(OR⁶)  (XVa)    wherein R¹, R², R⁶, x and y have the same meanings as defined above,    and then reacting the tri, di or monochlorosilane compound of the    formula (XVa) with a Grignard reagent of the formula (XVI)    (R^(3a))MgX  (XVI)    wherein R^(3a) stands for a secondary alkyl group, tertiary alkyl    group or a cycloalkyl group as defined above, or R^(3a) stands for    an alkyl-substituted aromatic hydrocarbon group of which alkyl    substituent is bonding to a carbon atom present in the aromatic    hydrocarbon group, with said carbon atom being adjacent to the    carbon atom of the aromatic hydrocarbon group that is bonding to the    magnesium atom, and X stands for chlorine, bromine or iodine atom.

As preferred examples of the chlorosilane compound of the formula (XIII)to be used for this Method (A), there may be mentionedtetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane,ethyltrichlorosilane, vinyltrichlorosilane, divinyldichlorosilane,phenyltrichlorosilane, diphenyldichlorosilane,vinylmethyldichlorosilane, phenylmethyldichlorosilane, and others.

The alcohol R⁶OH of the formula (XIV) to be reacted with thechlorosilane compound of the formula (XIII) includes a primary orsecondary alkyl alcohol or a cycloalkyl alcohol or an aralkyl alcohol.

Of the alcohol of the formula (XIV), the alkyl alcohol (an alkanol) mayconcretely be methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol, etc. The cycloalkyl alcohol may, for example,be cyclopentyl alcohol and cyclohexyl alcohol. The aralkyl alcohol may,for example, be benzyl alcohol, phenylethyl alcohol, etc.

The step of the alkoxylation or aralkyloxylation reaction comprisingreacting tetrachlorosilane or an organo-chlorosilane of the formula(XIII) with an alcohol of the formula (XIV) may preferably be done byusing 0.5-2 moles, particularly 0.5-1.5 moles, of the alcohol of theformula (XIV) per 1 mole of tetrachlorosilane or the organo-chlorosilaneof the formula (XIII).

The step of the alkoxylation or aralkyloxylation reaction may be carriedout in the absence of a solvent or in an aprotic organic solvent. As theaprotic organic solvent, there may be used either an ether solventusually used in the Grignard reactions, such as diethylether,tetrahydrofuran, or a hydrocarbon solvent such as hexane, toluene. Thesolvent may be used singly or in combination of two or more. Thealkoxylation or aralkyloxylation reaction may be effected at atemperature in the range of −10° C.-150° C., preferably 0° C. Thisalkoxylation or aralkyloxylation reaction with the alcohol of theformula (XIV) generates hydrogen chloride gas as a by-product, and so itis necessary to expel the hydrogen chloride gas from the reactionsystem.

After the completion of the alkoxylation or aralkyloxylation reaction,there is obtained a reaction solution containing a mono(alkoxy,cycloalkyloxy or aralkyloxy)-chlorosilane of the formula (XVa) thusproduced. The mono-organo-chlorosilane of the formula (XVa) may beseparated or recovered by subjecting the reaction solution to afractional distillation under an atmospheric pressure or a reducedpressure. Alternatively, the said reaction solution may be used as such,namely directly, in the subsequent Grignard reaction step.

Next, the mono(alkoxy, cycloalkyloxy or aralkyloxy)-chlorosilane of theformula (XVa) as obtained in the above step is reacted with a Grignardreagent of the general formula (XVI).

As concrete examples of the Grignard reagent of the formula (XVI), theremay be enumerated isopropyl magnesium chloride, isopropyl magnesiumbromide, isopropyl magnesium iodide; sec-butyl magnesium chloride,sec-butyl magnesium bromide, sec-butyl magnesium iodide; sec-pentylmagnesium chloride, sec-pentyl magnesium bromide and sec-pentylmagnesium iodide. Further examples of the Grignard reagent may includecyclopentyl magnesium chloride, cyclopentyl magnesium bromide,cyclopentyl magnesium iodide; cyclohexyl magnesium chloride, cyclohexylmagnesium bromide, cyclohexyl magnesium iodide; tert-butyl magnesiumchloride, tert-butyl magnesium bromide, tert-butyl magnesium iodide;1,1-dimethylpropyl magnesium chloride, 1,1-dimethylpropyl magnesiumbromide, 1,1-dimethylpropyl magnesium iodide; 1-methyl-1-ethylpropylmagnesium chloride, 1-methyl-1-ethylpropyl magnesium bromide,1-methyl-1-ethylpropyl magnesium iodide; 1,1-diethylpropyl magnesiumchloride, 1,1-diethylpropyl magnesium bromide, 1,1-diethylpropylmagnesium iodide; 1,1,2-trimethylpropyl magnesium chloride,1,1,2-trimethylpropyl magnesium bromide, 1,1,2-trimethylpropyl magnesiumiodide; 1-methylcyclopentyl magnesium chloride, 1-methylcyclopentylmagnesium bromide, 1-methylcyclopentyl magnesium iodide;1-methylcyclohexyl magnesium chloride, 1-methylcyclohexyl magnesiumbromide, 1-methylcyclohexyl magnesium iodide; 1-ethylcyclohexylmagnesium chloride, 1-ethylcyclohexyl magnesium bromide,1-ethylcyclohexyl magnesium iodide; o-tolyl magnesium chloride, o-tolylmagnesium bromide, o-tolyl magnesium iodide; 2,3-xylyl magnesiumchloride, 2,3-xylyl magnesium bromide, 2,3-xylyl magnesium iodide;2,4-xylyl magnesium chloride, 2,4-xylyl magnesium bromide, 2,4-xylylmagnesium iodide; 2,5-xylyl magnesium chloride, 2,5-xylyl magnesiumbromide, 2,5-xylyl magnesium iodide; 2,6-xylyl magnesium chloride,2,6-xylyl magnesium bromide, 2,6-xylyl magnesium iodide; mesitylmagnesium chloride, mesityl magnesium bromide, mesityl magnesium iodide;1-naphthyl magnesium chloride, 1-naphthyl magnesium bromide or1-naphthyl magnesium iodide. However, these examples do not limit thescope of the usable Grignard reagent.

The Grignard reaction above may be carried out in an ether solvent or ina mixed solvent of an ether solvent with an aprotic organic solvent. Asthe usable aprotic organic solvent, there may be mentioned a hydrocarbonsolvent such as hexane, heptane, toluene, xylene, etc. The Grignardreagent of the formula (XVI) may preferably be used for the intendedreaction in a proportion of 1-10 moles, preferably 1-5 moles per 1 moleof the mono(alkoxy, cycloalkyloxy or aralkyloxy)-chlorosilane of theformula (XVa). When the reaction solution as obtained in the precedingreaction step for the preparation of the compound of the formula (XVa)is used as such in the step of the Grignard reaction, it is usuallydesirable that the said Grignard reaction is carried out, if the solventis used for the Grignard reaction, in the ether solvent or the mixedsolvent of the ether solvent with the aprotic solvent which is same asthat used in the preceding reaction step. The Grignard reaction may beconducted at a temperature in the range of −10° C.-150° C., preferably20° C.-150° C. Further, this reaction is desirably carried out under aninert gas atmosphere such as nitrogen, argon, etc., because the presenceof oxygen in the reaction system may cause undesirable reaction of theGrignard reagent with oxygen, thus bringing about a decrease in theyield of the desired product.

The Grignard reaction may be carried out in a usual manner for 1-24hours up to the completion. Thereafter, the resulting reaction mixtureor solution is mixed with a suitable amount of a saturated aqueousammonium chloride solution or a dilute sulfuric acid, so that theinorganic magnesium salt as deposited in the reaction mixture can bedissolved in said aqueous ammonium chloride solution or the dilutesulfuric acid. The organic layer may then be separated from the aqueouslayer and subjected to a fractional distillation under an atmospheric orreduced pressure, so that there can be separated and recovered thefraction consisting of the desired tri-organo-mono(alkoxy, cycloalkyloxyor aralkyloxy)silane of the general formula (XIb).

-   (ii) Method (B) is adapted for the preparation of an    organo-unsubstituted or mono or    di-organo-mono(2-substituted-2-chloroethoxy)silane of the formula    (XIb-1)

wherein R¹, R², R^(3a) and R⁴ have the same meanings as defined above,which is included within the scope of the tri-organo-silane compound ofthe general formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb)which is to be used as a starting compound. This Method (B) comprisesreacting tetrachlorosilane or a di or mono-organo-di or trichlorosilaneformula (XIII)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XIII)wherein R¹ and R² have the same meanings as defined above and x and yare the integer as defined above, with an alkylene oxide or aglycidylether of the formula (XVII)

wherein R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, orR⁴ is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group, thereby to produce anorgano-unsubstituted or mono-organo or di-organo-mono(2-substituted orunsubstituted-2-chloroethoxy)-tri, di or monochloro-silane of theformula (XVb)

wherein R¹, R², R⁴, x and y have the same meanings as defined above, andthen reacting the chlorosilane compound of the formula (XVb) with aGrignard reagent of the formula (XVI)(R^(3a))MgX  (XVI)wherein R^(3a) stands for a secondary alkyl group, a tertiary alkylgroup or a cycloalkyl group as defined above, or R^(3a) is analkyl-substituted aromatic hydrocarbon group as defined above.

In case where the group R⁴ of the compound of the formula (XVII) used inMethod (B) is a hydrogen atom or an alkyl group, the alkylene oxide ofthe formula (XVII) is an epoxy compound having an epoxy group at the endthereof, such as ethylene oxide, propylene oxide, and the like.

In case where the group R⁴ of the compound of the formula (XVII) is analkoxymethylene group or an aryloxymethylene group, the compound of theformula (XVII) is a glycidylether, such as butylglycidylether,glycidylmethylether, etc. Another examples of the glycidylether of theformula (XVII) are 2-ethylhexylglycidylether, octadecylglycidylether,allylglycidylether and glycidylphenylether.

In Method (B), the reaction can proceed by reacting 0.5-2 moles of analkylene oxide or a glycidylether of the general formula (XVII) with 1mole of tetrachlorosilane or an organo-chlorosilane of the formula(XIII) in the absence of a solvent or in an aprotic organic solvent, forexample, diethylether at a temperature of −10° C.-150° C. Hydrocarbonsolvent may be used as a co-solvent. In contrast to Method (A), nohydrogen chloride gas is generated in Method (B), because the epoxygroup of the compound of the formula (XVII) can be ring-opened upon thereaction with the chlorosilane of the formula (XIII), whereby to uptaketherein the chloro group of the chlorosilane compound of the formula(XIII).

-   (iii) Method (C) is adapted for the preparation of a    tri-organo-silane compound of the formula (XIb) where the group Z²    in the formula (XIb) does not mean the 2-substituted or    unsubstituted-2-chloroethoxy group of the formula (A). This    Method (C) comprises adding to tetrachlorosilane or a di or    mono-organo-di or trichlorosilane of the formula (XIII)    (R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XIII)    wherein R¹ and R² have the same meanings as defined above and x and    y are the integer as defined above, an alkoxysilane of the formula    (XIX)    (R¹)_(x)(R²)_(y)Si(OR⁶)_(z)Cl_(4−(x+y+z))  (XIX)    wherein R¹, R² and R⁶ have the same meanings as defined above, x and    y each stand for an integer of 0, 1 or 2, but are to be within the    range of 0≦(x+y)≦2, and z stands for an integer of 2, 3 or 4, but is    to be within the range of 2≦(x+y+z)≦4, then effecting a    disproportionation reaction between the chlorosilane of the    formula (XIII) and the alkoxysilane of the formula (XIX) to produce    an alkoxychlorosilane, and further reacting the resulting    alkoxychlorosilane product with a Grignard reagent of the formula    (XVI), (R^(3a))MgX.

The groups R¹ and R² of the alkoxysilane of the formula (XIX) used forMethod (C) stand for the same substituents as R¹ and R² of the formula(XIa) or (XIII). Concrete examples of the alkoxysilane of the formula(XIX) may be tetramethoxysilane, tetraethoxysilane,methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,divinyldimethoxysilane, divinyldiethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,vinylmethyldimethoxysilane, vinylmethyldiethoxysilane,phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, and the like.

In the disproportionation reaction as effected in Method (C), thechlorosilane of the formula (XIII) and the alkoxysilane of the formula(XIX) are preferably reacted together in such a manner that 0.1-3 moles,particularly 0.2-1.5 moles of the alkoxysilanes of the formula (XIX) areused per 1 mole of the chlorosilane of the formula (XIII), so as to makethe proportion of the desired alkoxychlorosilane product to be producedat a maximum. The disproportionation reaction may be conducted in theabsence of a solvent at a temperature of 0° C.-50° C., preferably 10°C.-30° C.

The reaction solution resulting from the disproportionation reactionstep as above is in the form of a solution of mixed products whichcontains not only the desired organo-unsubstituted or mono ordi-organo-mono(alkoxy or cycloalkyloxy or aralkyloxy)-tri, di ormonochlorosilane compound as the main component, but also contains thestarting materials yet unreacted and some by-products formed byside-reactions, in which two or more of the chloro groups of thestarting chlorosilane compound (XIII) have been alkoxylated. Theorgano-chlorosilane product is then subjected to a Grignard reactionwith a Grignard reagent (XVI) in a next step. In this next step ofGrignard reaction, the reaction solution resulted from the precedingdisproportionation reaction step can be used as such. Otherwise, thesaid reaction solution is subjected to fractional distillation toisolate therefrom the desired mono(alkoxy or cycloalkyloxy oraralkyloxy)silane as a purified product, which is then used for the nextGrignard reaction step.

-   (iv) Method (D) is adapted for the preparation of a    tri-organo-silane compound of the general formula (XIb)    (R¹)(R²)(R^(3a))SiZ²  (XIb)    which is to be used as the starting compound. The Method (D)    comprises adding an alcohol of the formula (XIV)    (R⁶)OH  (XIV)    wherein R⁶ is a primary or secondary alkyl group, a cycloalkyl group    or an aralkyl group as defined above, or an alkylene oxide or a    glycidylether of the formula (XVII)

wherein R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms asshown above, or R⁴ is an alkoxymethylene group, an alkenyloxymethylenegroup or an aryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ isa straight or branched chain alkyl group of 1-20 carbon atoms or analkenyl group of 2-10 carbon atoms or an aryl group, to a Grignardreagent of the formula (XVI)(R^(3a))MgX  (XVI)wherein R^(3a) stands for a secondary alkyl group, a tertiary alkylgroup or a cycloalkyl group, or R^(3a) stands for an alkyl-substitutedaromatic hydrocarbon group of which said alkyl substituent is bonding toa carbon atom present in the aromatic hydrocarbon group, with saidcarbon atom being adjacent to the carbon atom of the aromatichydrocarbon group that is bonding to the magnesium atom, then effectingthe Grignard reaction therebetween, then adding to the solution formedof the resulting Grignard reaction mixture an amount oftetrachlorosilane or a di or mono-organo-di or trichlorosilane of theformula (XIII)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XIII)wherein R¹ and R², as defined in the formula (XI), are equal to eachother or are different from each other and each stand for a primary,secondary or tertiary alkyl group, a cycloalkyl group, an alkenyl group,an alkynyl group, an aralkyl group or an aryl group and x and y eachstand for an integer of 0, 1 or 2, but are to be within the range of0≦(x+y)≦2, then effecting the reactions between the reactive components,and then separating and recovering from the resulting reaction solutioncontaining the different reaction products, the desiredtri-organo-silane compound of the formula (XIb) above.

-   (v) Method (E) is adapted for the preparation of the starting    tri-organo-silane compound of the formula (XIb)    (R¹)(R²)(R^(3a))SiZ²  (XIb)    Method (E) comprises the steps of adding to the Grignard reagent of    the formula (XVI) as used in Method (D) above an amount of    tetrachlorosilane or a di or mono-organo-di or trichlorosilane of    the general formula (XIII) as used in Method (D) above, reacting    them with each other and subsequently adding to the so obtained    reaction mixture an amount of the alcohol of the formula (XIV) or    the alkylene oxide or glycidylether of the formula (XVII) as used in    Method (D), then reacting the reactive components with each other,    and finally recovering the desired tri-organo-silane compound of the    formula (XIb) from the resulting different reaction products so    formed.

The silane compound of the formula (XIa) or (XIb) as prepared by Method(A) to Method (E) mentioned above may be the one which has been isolatedfrom the reaction solution obtained in their preparation step, or may bethe one which still remains contained in such reaction solutionunpurified.

-   (vi) Method (F) is adapted for the preparation of a starting    tri-organo-silane compound of the formula (XIa)    (R¹)(R²)(R³)SiZ¹  (XIa)    Method (F) comprises reacting a tri-organo-hydrosilane compound of    the formula (XVIII)    (R¹)(R²)(R³)SiH  (XVIII)    wherein R¹, R² and R³ are the same as or different from each other    and each are a primary, secondary or tertiary alkyl group, a    cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl    group or an aryl group, and wherein all the groups R¹, R² and R³ are    not methyl group simultaneously, with an alcohol of the formula    (XIV)    R⁶OH  (XIV)    wherein R⁶ stands for a primary or secondary alkyl group, a    cycloalkyl group or an aralkyl group as defined above, in the    presence of an alkaline catalyst. By Method (F) above, there can be    produced a tri-organo-mono(alkoxy, cycloalkyloxy or    alkenyloxy)silane of the formula (XIa-1)    (R¹)(R²)(R³)Si(OR⁶)  (XIa-1)    wherein R¹, R², R³ and R⁶ have the same meanings as defined above.

In Method (F) above, the alkaline catalyst used may be an alkali metalhydroxide such as sodium hydroxide and potassium hydroxide, or a sodiumalcoholate of a lower alkanol such as sodium methylate and sodiumethylate. The reaction of the tri-organo-hydrosilane of the formula(XVIII) with the alcohol of the formula (XIV) may be conducted in analkanol solvent such as methanol or ethanol. The reaction may beeffected at a temperature from 20° C. to the refluxing temperature.

In case where the tri-organo-silane compound of the formula (XIa) to beused as a starting compound for the process according to the thirdaspect of this invention has a hydrolyzable group Z¹, thetri-organosilane compound (XIa) having such group Z¹ may be prepared bya process of synthesis using an alkyl orthosilicate and a Grignardreagent (see a Japanese book titled “Organic Silicon Chemistry”, p. 95and p. 242, edited jointly by Makoto Kumada and Rokuro Okawara) or by aprocess for synthesis of sulfate esters (see the book titled “OrganicSilicon Chemistry”, p. 291, edited jointly by Makoto Kumada and RokuroOkawara), or by a process for synthesis of amino, cyano, isocyano andisocyanato-silanes (see the book titled “Organic Silicon Chemistry”,edited jointly by Makoto Kumada and Rokuro Okawara).

According to the third aspect process of this invention, it is possibleto produce a tri-organo-monochlorosilane containing the bulkyhydrocarbon groups, by simple and convenient reaction procedures and ingood yield.

As mentioned above, the processes according to the first and secondaspects of this invention are now provided for the purpose of producingthe tri-organo-monoalkoxysilanes.

Apart from the processes of the first and second aspects of thisinvention, we now have also proceeded our further investigations for thepurpose of developing a new process capable of producing atri-organo-monoalkoxysilane containing the bulky hydrocarbon group orgroups such as a secondary alkyl group, a tertiary alkyl group, acycloalkyl group or an aryl group, by easy and safe reaction procedures.

As a result of our eager investigations made, we have now found that,when the chlorosilane of the above formula (I) to be used as thestarting compound is subjected to a reaction with the Grignard reagentof the above formula (II), and when a co-presence of an alcohol of theformula (XXIII) defined below or an epoxy compound of the formula (XXIV)defined below is provided in the reaction system of conducting suchreaction, there can progress the reaction of said alcohol or epoxidecompound with the Grignard reagent of the formula (II) to produce amagnesium alkoxide compound as an intermediate product, and saidintermediate product can then react with one of the chloro groups of thestarting chlorosilane of the formula (I), thereby to produce amonoalkoxy-chlorosilane, with involving such advantage that thereactivity of the remaining chloro groups in the resultingmonoalkoxy-chlorosilane as produced has been enhanced, and we have foundthat said monoalkoxychlorosilane as produced can then easily reactfurther with the Grignard reagent containing the secondary alkyl group,tertiary alkyl group, cycloalkyl group or alkyl-substituted aromatichydrocarbon group which is of a high steric hindrance in nature, wherebysuch secondary alkyl group, tertiary alkyl group or cycloalkyl group oralkyl-substituted aromatic hydrocarbon group can be introduced onto thesilicon atom of the monoalkoxychlorosilane. On the basis of thisfinding, we have accomplished a fourth aspect of this invention asdescribed below.

According to the fourth aspect of this invention, there is provided aprocess for the production of a tri-organo-mono(alkoxy, cycloalkyloxy oraralkyloxy)-silane containing a bulky hydrocarbon group or groups Rtherein and having the formula (XXVa)R_(3−(x+y))(R¹)_(x)(R²)_(y)Si(OR⁷)  (XXVa)wherein R¹ stands for a primary, secondary or tertiary alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an aryl group oran aralkyl group, R² stands for a secondary alkyl group, a tertiaryalkyl group, a cycloalkyl group or an aryl group, and wherein R standsfor a secondary alkyl group or a tertiary alkyl group or a cycloalkylgroup, or R stands for an alkyl-substituted aromatic hydrocarbon groupas defined below, and R⁷ has the same meaning as R³ defined below, or R⁷is a group of the formula —CH₂—CH(R)—R⁴ where R and R⁴ have the samemeaning as defined below, and x stands for an integer of 0 or 1 and ystands for an integer of 0, 1 or 2, where the integers for x and y areto be within the range of 0≦(x+y)≦2, characterized in that the processcomprises reacting tetrachlorosilane or a di or mono-organo-di ortrichlorosilane of the formula (XXI)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XXI)wherein R¹ and R² have the same meanings as defined above and x and yeach stand for an integer as defined above, with a Grignard reagent ofthe formula (XXII)RMgX  (XXII)wherein R stands for a secondary alkyl group or a tertiary alkyl groupor a cycloalkyl group, or R stands for an alkyl-substituted aromatichydrocarbon group of which the alkyl substituent is bonding to a carbonatom present in the aromatic hydrocarbon group, with said carbon atombeing adjacent to the carbon atom of the aromatic hydrocarbon group thatis bonding to the magnesium atom, and X stands for a chlorine, bromineor iodine atom, in a manner such that the reaction of tetrachlorosilaneor the di or trichlorosilane of the formula (XXI) with the Grignardreagent of the formula (XXII) is effected with addition of and reactionwith an alcohol of the formula (XXIII)R³OH  (XXIII)wherein R³ stands for a primary or secondary alkyl group, a cycloalkylgroup or an aralkyl group, or an alkylene oxide or a glycidylether ofthe formula (XXIV)

wherein R⁴ stands for a hydrogen atom or an alkyl group of 1-8 carbonatoms, or R⁴ stands for an alkoxymethylene group, an alkenyloxymethylenegroup or an aryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ isa straight or branched chain alkyl group of 1-20 carbon atoms, analkenyl group of 2-10 carbon atoms or an aryl group.

In tetrachlorosilane or the di or mono-organo-di or trichlorosilane ofthe formula (XXI)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XXI)which is to be used in the fourth aspect process of this invention, R¹stands for a primary, secondary or tertiary alkyl group, a cycloalkylgroup, an alkenyl group, an alkynyl group, an aryl group or an aralkylgroup and R² stands for a secondary alkyl group, a tertiary alkyl group,a cycloalkyl group or an aryl group as shown above.

The primary, secondary or tertiary alkyl group for the substituent R¹ inthe chlorosilane compound of the formula (XXI) above is preferably astraight or branched chain alkyl group of 1-10 carbon atoms, andconcrete examples thereof may include methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group,sec-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, n-heptylgroup, n-octyl group, 2-ethylhexyl group, n-dodecyl group andn-octadecyl group. The cycloalkyl group for R¹ may be those of 3-8carbon atoms such as cyclopentyl group and cyclohexyl group.

As the alkenyl group for R¹ in the formula (XXI), there may beexemplified vinyl group, methallyl group, allyl group and the like. Asthe alkynyl group for R¹, there are ethynyl group, 1-propynyl group andthe like. As the aryl group for R¹, there are, for example, phenylgroup, an alkyl-substituted phenyl group such as o-tolyl group, m-tolylgroup, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, mesityl group, or1-naphthyl group, and the like. As the aralkyl group for R¹, there arementioned a lower alkyl group substituted with phenyl group, such asbenzyl group, phenylethyl group (i.e. phenethyl group) and the like.

The secondary alkyl group for R² in the formula (XXI) is those of 3-10carbon atoms, examples of which may include isopropyl group, sec-butylgroup, sec-pentyl group and the like. The tertiary alkyl group for R² isthose of 4-10 carbon atoms, examples of which may include tert-butylgroup, 1,1-dimethylpropyl group, 1-ethyl-1-methylpropyl group,1,1,2-trimethylpropyl group and 1,1-diethylpropyl group.

The cycloalkyl group for R² in the formula (XXI) may be those of 3-8carbon atoms such as cyclopentyl group and cyclohexyl group. The arylgroup for R² may be the same as those exemplified as R¹ above.

As preferred examples of the chlorosilane compound of the formula (XXI),there are mentioned tetrachlorosilane, methyltrichlorosilane,ethyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane,diphenyldichlorosilane, phenylmethyldichlorosilane and the like.

In the organo-metallic compound RMgX which is to be used as the Grignardreagent of the formula (XII) in the fourth aspect process of thisinvention, the bulky hydrocarbon group R contained therein is asecondary or tertiary alkyl group or a cycloalkyl group, or analkyl-substituted aromatic hydrocarbon group. Examples of the secondaryalkyl group for R may include isopropyl group, sec-butyl group,sec-pentyl group and the like. Examples of the tertiary alkyl group forR may include tert-butyl group, 1,1-dimethylpropyl group,1-methyl-1-ethylpropyl group, 1,1-diethylpropyl group,1,1,2-trimethylpropyl group and the like. As the cycloalkyl group, thereare exemplified cyclopentyl group, cyclohexyl group, 1-methylcyclopentylgroup, 1-methylcyclohexyl group, 1-ethylcyclohexyl group and the like.

As the alkyl-substituted aromatic hydrocarbon group for R, there areexemplified an alkyl-substituted phenyl group such as o-tolyl group,2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group,mesityl group or 1-naphthyl group and the like. The group X stands for ahalogen group being chlorine, bromine or iodine.

As concrete examples of the Grignard reagent of the formula (XXII),there may be enumerated isopropyl magnesium chloride, isopropylmagnesium bromide, isopropyl magnesium iodide; sec-butyl magnesiumchloride, sec-butyl magnesium bromide, sec-butyl magnesium iodide;sec-pentyl magnesium chloride, sec-pentyl magnesium bromide, sec-pentylmagnesium iodide; and cyclopentyl magnesium chloride, cyclopentylmagnesium bromide, cyclopentyl magnesium iodide; cyclohexyl magnesiumchloride, cyclohexyl magnesium bromide, cyclohexyl magnesium iodide;tert-butyl magnesium chloride, tert-butyl magnesium bromide, tert-butylmagnesium iodide; 1,1-dimethylpropyl magnesium chloride,1,1-dimethylpropyl magnesium bromide, 1,1-dimethylpropyl magnesiumiodide; 1-methyl-1-ethylpropyl magnesium chloride,1-methyl-1-ethylpropyl magnesium bromide, 1-methyl-1-ethylpropylmagnesium iodide; 1,1-diethylpropyl magnesium chloride,1,1-diethylpropyl magnesium bromide, 1,1-di-ethylpropyl magnesiumiodide; and 1,1,2-trimethylpropyl magnesium chloride,1,1,2-trimethylpropyl magnesium bromide, 1,1,2-trimethylpropyl magnesiumiodide; and 1-methylcyclopentyl magnesium chloride, 1-methyl-cyclopentylmagnesium bromide, 1-methylcyclopentyl magnesium iodide;1-methylcyclohexyl magnesium chloride, 1-methylcyclohexyl magnesiumbromide, 1-methylcyclohexyl magnesium iodide; 1-ethylcyclohexylmagnesium chloride, 1-ethylcyclohexyl magnesium bromide,1-ethylcyclohexyl magnesium iodide; and o-tolyl magnesium chloride,o-tolyl magnesium bromide, o-tolyl magnesium iodide; 2,3-xylyl magnesiumchloride, 2,3-xylyl magnesium bromide, 2,3-xylyl magnesium iodide;2,4-xylyl magnesium chloride, 2,4-xylyl magnesium bromide, 2,4-xylylmagnesium iodide; 2,5-xylyl magnesium chloride, 2,5-xylyl magnesiumbromide, 2,5-xylyl magnesium iodide; 2,6-xylyl magnesium chloride,2,6-xylyl magnesium bromide, 2,6-xylyl magnesium iodide; mesitylmagnesium chloride, mesityl magnesium bromide, mesityl magnesium iodide;1-naphthyl magnesium chloride, 1-naphthyl magnesium bromide and1-naphthyl magnesium iodide, but these particular examples do not limitthe scope of the usable Grignard reagent.

The alcohol R³OH of the formula (XXIII) to be used in the fourth aspectprocess of this invention is a primary or secondary alkylalcohol or acycloalkylalcohol or an aralkylalcohol.

Of the alcohol of the formula (XXIII), the alkylalcohol (alkanol) maytypically be methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol and the like. The cycloalkyl alcohol maytypically be cyclopentyl alcohol and cyclohexyl alcohol, and the aralkylalcohol may typically be benzyl alcohol, phenylethyl alcohol and thelike.

Further, in respect of the alkylene oxide or glycidylether (i.e. epoxycompound as above) which may be used according to the fourth aspectprocess of this invention and which is of the formula (XXIV)

wherein R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, orR⁴ stands for an alkoxymethylene group, an alkenyloxymethylene group oran aryloxymethylene group of the formula —CH₂—O—R⁵ where R⁵ is astraight or branched chain alkyl group of 1-20 carbon atoms or analkenyl group of 2-10 carbon atoms or an aryl group, said compound ofthe formula (XXIV) is an alkylene oxide, when R⁴ is a hydrogen atom oran alkyl group, namely an epoxy compound having an epoxy group at theend thereof. The alkylene oxide may be ethylene oxide, propylene oxideand the like.

On the other hand, when R⁴ of the epoxy compound of the formula (XXIV)is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxymethylene group, said epoxy compound of the formula (XXIV) is aglycidylether. Examples of the glycidylether may be butylglycidylether,glycidylmethylether and the like. Further examples of the glycidylethermay include 2-ethylhexylglycidylether, octadecylglycidylether;allylglycidylether; and glycidylphenylether.

As mentioned above, the process according to the fourth aspect of thisinvention comprises effecting the reaction of the chlorosilane compoundof the formula (XXI) with the Grignard reagent of the formula (XXII), ina manner such that said reaction is carried out with making addition ofthe alcohol of the formula (XXIII) or the epoxy compound of the formula(XXIV) (more concretely an alkylene oxide or a glycidyl ether) uponstarting such reaction, so that the alcohol (XXIII) or the epoxycompound (XXIV) will participate in the reactions with the Grignardreagent and said chlorosilane compound.

The fourth aspect process of this invention may be carried out inaccordance with Procedure (A) or Procedure (B) as explained in (i)-(ii)below, respectively.

-   (i) In Procedure (A), the reaction of the chlorosilane of the    formula (XXI) with the Grignard reagent of the formula (XXII) is    effected by admixing and reacting the Grignard reagent of the    formula (XXXII) with the alcohol of the formula (XXIII) or the    alkylene oxide or glycidylether of the formula (XXIV), then adding    to the so obtained reaction mixture containing therein the remaining    Grignard reagent and the resulting reaction product of the reaction    of the Grignard reagent with the alcohol or the alkylene oxide or    glycidylether    an amount of tetrachlorosilane or a di or mono-organo-di or    trichlorosilane of the formula (XXI), and effecting further    reactions between the Grignard reagent, said reaction product and    the added tetrachlorosilane or the added di or mono-organo-di or    trichlorosilane present in the resultant mixture, to produce the    tri-organo-mono-(alkoxy, cycloaekyloxy or aralkyloxy)silane of    formula (XXVa). In this procedure (A), it is preferable to use and    add 0.5-2 moles, particularly 0.5-1.5 moles of the alcohol of the    formula (XXIII) or the epoxy compound of the formula (XXIV) per 1    mole of the chlorosilane compound of the formula (XXI) for effecting    the reaction. It is also preferable that the Grignard reagent of the    formula (XXII) is used in a proportion of 1-10 moles, particularly    2-5 moles per 1 mole of the chlorosilane compound of the    formula (XXI) for effecting the reaction.

As mentioned above, in Procedure (A), the reaction is at first effectedby admixing and reacting at first the Grignard reagent of the formula(XXII) with the alcohol of the formula (XXIII) or the epoxy compound ofthe formula (XXIV) (i.e. alkylene oxide or glycidylether). The soobtained reaction mixture or solution contains, as an intermediatereaction product, an alkoxy-, cycloalkyloxy- or aralkyloxy-magnesiumhalide of the formula (XXVIa)(R³O)MgX  (XXVIa)wherein R³ and X have the same meanings as defined above, which has beenformed by the reaction of the Grignard reagent of the formula (XXII)with the alcohol of the formula (XXIII), or alternatively the saidreaction mixture or solution contains a 2-substituted-ethoxy-magnesiumhalide of the formula (XXVIb)

wherein R, R⁴ and X have the same meanings as defined above, which hasbeen formed by the reaction of the Grignard reagent of the formula(XXII) with the epoxy compound of the formula (XXIV).

The above alkoxy-substituted magnesium halide compound of the formula(XXVIa) or the formula (XXVIb), which has thus been produced as theintermediate reaction product, is further reacted with the chlorosilanecompound of the formula (XXI) to produce an intermediate chlorosilanederivative which is formed by the replacement of one of the chloro groupof said chlorosilane compound (XXI) by the group R³O— or the groupR⁴—CHR—CH₂—O— present in the formula (XXVIa) or (XXVIb).

Said intermediate chlorosilane derivative thus produced may be either anorgano-unsubstituted or mono or di-organo-mono(alkoxy, cycloalkyloxy oraralkyloxy)-tri, di or monochlorosilane of the formula (XXVIIa)(R¹)_(x)(R²)_(y)SiCl_(3−(x+y))—(OR³)  (XXVIIa)wherein R¹, R², R³, x and y have the same meanings as defined above, oran organo-unsubstituted or mono ordi-organo-mono(2-substituted-ethoxy)-tri, di or monochlorosilane of theformula (XXVIIb)

wherein R, R¹, R², R⁴, x and y have the same meanings as defined above.

The remaining chloro group or groups of the resulting tri, di ormonochlorosilane derivative of the above formula (XXVIIa) or (XXVIIb)once produced as the above intermediate product can further be reactedwith the Grignard reagent of the formula (XXII) in the same manner as inthe processes of the first and second aspects of this invention. By thisfurther latter Grignard reaction, consequently there is formed thetri-organo-monoalkoxysilane of the above formula (XXVa) which is thetarget product of the fourth aspect process of this invention. Further,in Procedure (A), an amount of the remaining unreacted Grignard reagentof the formula (XXII) still existing in the reaction mixture or systemcan also react directly with one to two chloro groups of the startingchlorosilane compound (XXI) as added later, and thus there proceedsconcurrently some reaction of another route for the production oforgano-chlorosilane derivatives which contain one to two groups of thesecondary alkyl group, tertiary alkyl group, a cycloalkyl group or anaryl group for R. Some other different side-reactions can also occurconcurrently.

-   (ii) Next, in Procedure (B) of the fourth aspect process of this    invention, the reaction of the chloro silane of the formula (XXI)    with the Grignard reagent of the formula (XXII) is effected by    admixing and reacting at first the Grignard reagent of the    formula (XXII) with tetrachlorosilane or a di or mono-organo-di or    trichlorosilane of the formula (XXI), then adding to the so obtained    reaction mixture containing therein the Grignard reagent and the    resulting reaction product of the reaction of the Grignard reagent    with tetrachlorosilane or the di or mono-organo-di or    trichlorosilane an amount of the alcohol of the formula (XXIII) or    the alkylene oxide or glycidylether of the formula (XXIV), and    effecting further reactions between the Grignard reagent, said    reaction product and the added alcohol or the added alkylene oxide    or glycidylether present in the resultant mixture, to produce the    tri-organo-mono-(alkoxy, cycloalkyloxy or aralkyloxy) silane of the    formula (XXVa).

In this Procedure (B), too, the Grignard reagent of the formula (XXII)is to be used in a proportion of 1-10 moles, preferably 2-5 moles per 1mole of the chlorosilane compound (XXI) for effecting the reaction. Thealcohol (XXIII) or the epoxy compound (XXIV) is to be used in aproportion of 0.5-2 moles, preferably 0.5-1.5 moles per 1 mole of thechlorosilane compound (XXI) for effecting the reaction.

In this Procedure (B), it is possible to take either the routecomprising adding the chlorosilane compound (XXI) to the Grignardreagent of the formula (XXII) and then effecting the reactions, or theroute comprising adding the Grignard reagent of the formula (XXII) tothe chlorosilane compound (XXI) and then effecting the reactions. Inboth the routes, in the resulting reaction mixture or solution, therehas been formed a chlorosilane derivative which has been produced as theintermediate reaction product by the direct reaction of the Grignardreagent of the formula (XXII) with the chlorosilane compound (XXI). Whenthe alcohol (XXIII) or the epoxy compound (XXIV) is then later added tothe said resulting reaction mixture or solution as above, said alcoholor epoxy compound as added can presumably be reacted with an amount ofthe remaining unreacted Grignard reagent of the formula (XXII). It isfurther presumable that the later occurring reaction will produce thealkoxy-magnesium halide of the formula (XXVIa) or (XXVIb) similarly tothat in the Procedure (A) above, and that the alkoxy-magnesium halidethus produced can further be reacted with the chlorosilane compound(XXI), thereby to produce the aforesaid intermediate chlorosilanederivative (XXVIIa) or (XXVIIb). Thus, consequently thetri-organo-monoalkoxysilane of the formula (XXVa), which is the targetproduct of the fourth aspect process of this invention, is producedthrough various routes by the Grignard reaction.

In the fourth aspect process of this invention, by either one ofProcedure (A) and Procedure (B), the reactions in the process may becarried out in an ether solvent or in a mixed solvent of an ethersolvent with an aprotic organic solvent. As the ether solvent, there maybe mentioned, for example, diethylether, tetrahydrofuran, and the like.As the aprotic organic solvent, there may be used a hydrocarbon solventsuch as hexane, heptane, toluene, xylene and the like.

The reactions may be conducted at a temperature in the range of 0-150°C., preferably 30-150° C. Further, it is preferable to carry out thereactions under an inert gas atmosphere such as nitrogen, argon and thelike, because the presence of oxygen in the reaction system brings aboutundesirable reaction of oxygen with the Grignard reagent, resulting inlowering of the yield of the desired target product.

In the fourth aspect process of this invention, the reactions with theGrignard reagent is conducted as usual for 1-24 hours until a completionof the reaction. Subsequently, a suitable amount of a saturated aqueousammonium chloride solution or dilute sulfuric acid is mixed with thefinal reaction mixture or solution as obtained after the completion ofthe reaction, so that the deposited inorganic magnesium salt can bedissolved in the aqueous ammonium chloride solution or in the dilutesulfuric acid. The organic layer in the reaction solution is thenseparated from the resulting aqueous layer, and the organic layer asseparated is subjected to a fractional distillation (that is,rectification) under an atmospheric or reduced pressure, and thus therecan be isolated and recovered the desired tri-organo-mono(2-substitutedor unsubstituted alkoxy or cycloalkyloxy or aralkyloxy)silane of theformula (XXVa).

By the way, when the reaction is effected with using such Grignardreagent of the formula (XXII) which contains a highly bulky tertiaryalkyl group such as tert-butyl group, there is a possibility that thedesired tri-tert-alkyl-substituted-mono(alkoxy, cycloalkyloxy oraralkyloxy)-silane would be produced only in a very low yield, even ifthe reaction has been effected for a long period of time.

The tri-organo-mono(alkoxy, cycloalkyloxy or aralkyloxy)silane of theformula (XXVa) may alternatively be represented by the formula (XVa-1)

wherein R¹, R², R, x and y each have the same meanings as defined in theformulae (XXI), (XXII) and (XXIII) above, and R⁷ has the same meaning asR³ of the formula (XXIII) above, or R⁷ is the group of the formula—CH₂—CH(R)—R⁴ where R and R⁴ have the same meanings as defined above.

Concrete examples of the tri-organo-mono(alkoxy, cycloalkyloxy oraralkyloxy)silane derivative of the formula (XXVa) as produced by thefourth aspect process of this invention may includetriisopropylmethoxysilane, triisopropylethoxysilane,triisopropylisopropoxysilane, triisopropyl-n-butoxysilane,triisopropyl-3-methylbutoxysilane, triisopropylbenzyloxysilane,tri-sec-butylmethoxysilane, tri-sec-butylethoxysilane,tri-sec-butylisopropoxysilane, tri-sec-butyl-n-butoxysilane,tri-sec-butyl-3-methylpentyloxysilane, tri-sec-butylbenzyloxysilane; andtricyclohexylmethoxysilane, tricyclohexylethoxysilane,tricyclohexylisopropoxysilane, tricyclohexyl-n-butoxysilane,tricyclohexyl-2-cyclohexylethoxysilane, tricyclohexylbenzyloxysilane;and tri-o-tolylmethoxysilane, tri-o-tolylethoxysilane,tri-o-tolylisopropoxysilane, tri-o-tolyl-n-butoxysilane,tri-o-tolyl-2-o-tolylethoxysilane, tri-o-tolylbenzyloxysilane;diisopropylmethylmethoxysilane, diisopropylmethylethoxysilane,diisopropylmethylisopropoxysilane, diisopropylmethyl-n-butoxysilane,diisopropylmethyl-3-methylbutoxysilane,diisopropylmethylbenzyloxysilane, diisopropylvinylmethoxysilane,diisopropylvinylethoxysilane, diisopropylvinylisopropoxysilane,diisopropylvinyl-n-butoxysilane, diisopropylvinyl-3-methylbutoxysilane,diisopropylvinylbenzyloxysilane, diisopropylphenylmethoxysilane,diisopropylphenylethoxysilane, diisopropylphenylisopropoxysilane,diisopropylphenyl-n-butoxysilane,diisopropylphenyl-3-methylbutoxysilane,diisopropylphenylbenzyloxysilane, di-sec-butylmethylmethoxysilane,di-sec-butylmethylethoxysilane, di-sec-butylmethylisopropoxysilane,di-sec-butylmethyl-n-butoxysilane,di-sec-butylmethyl-3-methylpentyloxysilane,di-sec-butylmethylbenzyloxysilane, di-sec-butylvinylmethoxysilane,di-sec-butylvinylethoxysilane, di-sec-butylvinylisopropoxysilane,di-sec-butylvinyl-n-butoxysilane,di-sec-butylvinyl-3-methylpentyloxysilane,di-sec-butylvinylbenzyloxysilane, di-sec-butylphenylmethoxysilane,di-sec-butylphenylethoxysilane, di-sec-butylphenylisopropoxysilane,di-sec-butylphenyl-n-butoxysilane,di-sec-butylphenyl-3-methylpentyloxysilane,di-sec-butylphenylbenzyloxysilane, dicyclohexylmethylmethoxysilane,dicyclohexylmethylethoxysilane, dicyclohexylmethylisopropoxysilane,dicyclohexylmethyl-n-butoxysilane,di-cyclohexylmethyl-2-cyclohexylethoxysilane,dicyclohexylmethylbenzyloxysilane, dicyclohexylvinylmethoxysilane,dicyclohexylvinylethoxysilane, dicyclohexylvinylisopropoxysilane,dicyclohexylvinyl-n-butoxysilane,dicyclohexylvinyl-2-cyclohexylethoxysilane,dicyclohexylvinylbenzyloxysilane, dicyclohexylphenylmethoxysilane,dicyclohexylphenylethoxyilane, dicyclohexylphenylisopropoxysilane,dicyclohexylphenyl-n-butoxysilane,dicyclohexylphenyl-2-cyclohexylethoxysilane,dicyclohexylphenylbenzyloxysilane, di-o-tolylmethylmethoxysilane,di-o-tolylmethylethoxysilane, di-o-tolylmethylisopropoxysilane,di-o-tolylmethyl-n-butoxysilane, di-o-tolylmethyl-2-o-tolylethoxysilane,di-o-tolylmethylbenzyloxysilane, di-o-tolylvinylmethoxysilane,di-o-tolylvinylethoxysilane, di-o-tolylvinylisopropoxysilane,di-o-tolylvinyl-n-butoxysilane, di-o-tolylvinyl-2-o-tolylethoxysilane,di-o-tolylvinylbenzyloxysilane, di-o-tolylphenylmethoxysilane,di-o-tolylphenylethoxysilane, di-o-tolylphenylisopropoxysilane,di-o-tolylphenyl-n-butoxysilane, di-o-tolylphenyl-2-o-tolylethoxysilane,di-o-tolylphenylbenzyloxysilane, isopropyldiphenylmethoxysilane,isopropyldiphenylethoxysilane, isopropyldiphenylisopropoxysilane,isopropyldiphenyl-n-butoxysilane,isopropyldiphenyl-3-methylbutoxysilane,isopropyldiphenylbenzyloxysilane, sec-butyldiphenylmethoxysilane,sec-butyldiphenylethoxysilane, sec-butyldiphenylisopropoxysilane,sec-butyldiphenyl-n-butoxysilane,sec-butyldiphenyl-3-methylpentyloxysilane,sec-butyldiphenylbenzyloxysilane, cyclohexyldiphenylmethoxysilane,cyclohexyldiphenylethoxysilane, cyclohexyldiphenylisopropoxysilane,cyclohexyldiphenyl-n-butoxysilane,cyclohexyldiphenyl-2-cyclohexylethoxysilane,cyclohexyldiphenylbenzyloxysilane, o-tolyldiphenylmethoxysilane,o-tolyldiphenylethoxysilane, o-tolyldiphenylisopropoxysilane,o-tolyldiphenyl-n-butoxysilane, o-tolyldiphenyl-2-o-tolylethoxysilane,o-tolyldiphenylbenzyloxysilane, tert-butyldiphenylmethoxysilane,tert-butyldiphenylethoxysilane, tert-butyldiphenylisopropoxysilane,tert-butyldiphenyl-n-butoxysilane,tert-butyldiphenyl-3,3-dimethylbutoxysilane,tert-butyldiphenylbenzyloxysilane, tert-butylphenylmethylmethoxysilane,tert-butylphenylmethylethoxysilane,tert-butylphenylmethylisopropoxysilane,tert-butylphenylmethyl-n-butoxysilane,tert-butylphenylmethyl-3,3-dimethylbutoxysilane, and the like, but thisparticular examples do not limit the scope of the object silane productof the formula (XXVa) in any way.

Of the silane product which can be produced by the fourth aspect processof this invention, triisopropylmonoalkoxysilane,tri-sec-butyl-monoalkoxysilane, tricyclohexylmonoalkoxysilane andtert-butyldimethylmonoalkoxysilane are particularly useful as a startingmaterial for the synthesis of tri-organo-chlorosilanes which are to beused as the silylating agent for protecting a functional hydroxyl groupof various synthetic intermediates that are produced in the preparationof medicines and the like. They are also useful in other applications.

According to the production process of the fourth aspect of thisinvention which needs only the facile operations for the reaction, therecan be produced a tri-organo-monoalkoxy or cycloalkyloxy oraralkyloxysilane compound containing the bulky hydrocarbon group orgroups and having the general formula (XXVa) in a high yield without anynecessity of using the lithium catalyst difficult to handle, and withoutany necessity of using any highly toxic catalyst.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the processes according to the first and second aspects of thisinvention are illustrated by Examples 1-10 and Example 43.

EXAMPLE 1

(a) Preparation of a Monoalkoxy-trichlorosilane as the Starting Compound

A four-necked flask (200 ml-capacity) fitted with a stirrer, athermometer and a Dimroth was charged with 102 g (0.6 moles) oftetrachlorosilane (namely, silicon tetrachloride). To the flask was thenadded dropwise 44 g (0.6 moles) of n-butanol over 1 hour at atemperature of 10° C.-25° C. in the flask. The resulting reactionmixture was then heated under stirring at a temperature of 60° C.-70° C.for 1 hour. There was obtained a reaction solution containingn-butoxytrichlorosilane as produced. This reaction solution wassubjected to a rectification (a fractional distillation) under a reducedpressure. Thus, there was afforded 50 g of n-butoxytrichlorosilane (oneexample of the compounds of the general formula (I)) as a fractionboiling at 66° C.-74° C./62 mm Hg.

Analysis of this product by a gas chromatography showed the purity of98%.

(b) Preparation of a Grignard Reagent

A four-necked flask (one-liter-capacity) fitted with a stirrer, athermometer and a Dimroth was charged with 16.0 g (0.66 moles) ofmetallic magnesium, 270 ml of an organic solvent, tetrahydrofuran, and asmall amount of iodine. To the resulting mixture was added dropwise 51.8g (0.66 moles) of isopropyl chloride under a nitrogen gas atmosphere ata temperature of 40° C.-50° C. in the flask over 1 hour. The resultingreaction mixture was then heated under stirring at 50° C. for 1 hour,thus affording a reaction solution containing isopropyl magnesiumchloride (the Grignard reagent) as produced.

(c) Grignard Reaction

To the solution in tetrahydrofuran (THF) of isopropyl magnesium chloride(the Grignard reagent) as obtained in (b) above was added dropwise 41.5g (0.2 moles) of the n-butoxytrichlorosilane produced in (a) above, at30° C.-40° C. over 1 hour. To the resulting reaction mixture was thenadded 150 ml of toluene, and the mixture so obtained was stirred at atemperature of 90° C. in the flask for 4 hours to conduct the Grignardreaction. To the resulting Grignard reaction solution was added dropwise120 ml of a saturated aqueous ammonium chloride solution to dissolve theprecipitated magnesium salt (MgCl₂). The resulting mixture was thenseparated into an aqueous layer and an organic layer. The organic layerwas subjected to a distillation, and thus, 42 g oftriisopropyl-n-butoxysilane was isolated as a fraction boiling at 96°C.-103° C./12 mm Hg (yield; 90%).

EXAMPLE 2

A Grignard reagent was prepared in accordance with the procedure ofExample 1 (b), except that 61.1 g (0.66 moles) of sec-butyl chloride wasused instead of isopropyl chloride. The sec-butyl magnesium chloridethus obtained was reacted with 105 g (0.2 moles) ofn-butoxytrichlorosilane in the same manner as in Example 1(b) for theintended Grignard reaction. Thus, 49 g of tri-sec-butyl-n-butoxysilanewas obtained as a fraction boiling at 106° C.-108° C./3 mm Hg (yield;88%).

EXAMPLE 3

(a) Preparation of Grignard Reagent

A four-necked flask (500 ml-capacity) fitted with a stirrer, athermometer and a Dimroth was charged with 16.0 g (0.66 moles) ofmetallic magnesium, 270 ml of tetrahydrofuran (THF) as an organicsolvent and a small amount of iodine. To the resulting mixture was addeddropwise 51.8 g (0.66 moles) of isopropyl chloride under a nitrogen gasatmosphere over 1 hour. During the dropwise addition, the reactionmixture in the flask was maintained at a temperature of 40° C.-50° C.Then, the reaction mixture was heated under stirring at 50° C. for 1hour, to obtain a THF solution of isopropyl magnesium chloride.

(b) Preparation of a Monoalkoxy-trichlorosilane as the Starting Compound

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 34.0 g (0.2 moles) oftetrachlorosilane, to which was then added dropwise 6.4 g (0.2 moles) ofmethanol over 1 hour. During the dropwise addition, the mixture in theflask was maintained at 10° C.-25° C. Then, the reaction mixture in theflask was heated under stirring at 50° C. for 1 hour. Thus, there wasobtained a reaction solution containing methoxytrichlorosilane asproduced.

(c) Grignard Reaction

The THF solution of isopropyl magnesium chloride (Grignard reagent) asprepared in (a) above was added dropwise through a dropping funnel to asolution containing methoxytrichlorosilane, that is, the reactionsolution as obtained in (b) above, at 30° C.-40° C. over 1 hour. Then,to the resulting mixture was added 150 ml of toluene, and the mixturewas stirred at a temperature of 90° C. in the flask for 4 hours toconduct the Grignard reaction. Then, 120 ml of a saturated aqueousammonium chloride solution was added dropwise to the resulting Grignardreaction solution to dissolve the magnesium salt. The organic layer wasseparated from the aqueous layer and then subjected to a fractionaldistillation under a reduced pressure, thus yielding 27 g oftriisopropylmethoxysilane as a fraction boiling at 85° C.-86° C./20 mmHg (yield; 70%).

EXAMPLE 4

8.8 g (0.2 moles) of ethylene oxide was used in place of methanol asused in Example 3 (b) and was reacted with 34.0 g of tetrachlorosilanein the same manner as in Example 3(b). Thus, there was obtained areaction solution containing 2-chloroethoxytrichlorosilane. Then, aGrignard reaction was effected by adding the THF solution of isopropylmagnesium chloride to the 2-chloroethoxytrichlorosilane in the samemanner as in Example 3 (c). The post-treatment of the Grignard reactionsolution so obtained was carried out in the same manner as in Example 3(c), and the separated organic layer was distilled to afford 48 g oftriisopropyl-2-chloroethoxysilane as a fraction boiling at 118° C.-120°C./5 mm Hg (yield; 71%).

EXAMPLE 5

61.1 g (0.66 moles) of sec-butyl chloride was used in place of isopropylchloride as used in Example 3(a), and the reaction of it with 16.0 g ofmetallic magnesium in THF was conducted in the same manner as in Example3(a). Thus, there was obtained a THF solution of sec-butyl magnesiumchloride. This THF solution of the Grignard reagent was added dropwiseto the methoxytrichlorosilane solution as prepared in Example 3(b), inthe same manner as in Example 3(c) to effect the Grignard reaction.

The resulting Grignard reaction solution was post-treated with asaturated aqueous ammonium chloride solution in the same manner as inExample 3 (c). The organic layer was separated from the aqueous layerand was fractionally distilled under a reduced pressure to afford 32 gof tri-sec-butylmethoxysilane as a fraction boiling 88° C.-91° C./5 mmHg (yield; 68%).

EXAMPLE 6

78.3 g (0.66 moles) of cyclohexyl chloride was used in place ofisopropyl chloride as used in Example 3(a) and was reacted with 16.0 gof metallic magnesium in THF in the same manner as in Example 3(a).There was thus obtained a THF solution of cyclohexyl magnesium chloride.

On the other hand, 14.8 g (0.2 moles) of n-butanol was used in place ofmethanol as used in Example 3(b) and was reacted with 34.0 g oftetrachlorosilane in the same manner as in Example 3(b). There was thusobtained a solution of n-butoxytrichlorosilane.

The THF solution of cyclohexyl magnesium chloride (Grignard reagent) asprepared above was added dropwise to the n-butoxytrichlorosilanesolution as prepared above, in the same manner as in Example 3(c),followed by effecting the Grignard reaction.

The resulting Grignard reaction solution was post-treated with asaturated aqueous ammonium chloride solution in the same manner as inExample 3(c). The organic layer was separated from the aqueous layer.The solvent was distilled off under a reduced pressure from the organiclayer, to afford crude crystals of tricyclohexyl-n-butoxysilane.Recrystallization from hexane gave 47 g of tricyclohexyl-n-butoxysilane(yield; 65%).

EXAMPLE 7

The reaction of Example 3(a) was repeated except that the metallicmagnesium was used in an amount of 10.7 g (0.44 moles) instead of 16.0 g(0.66 moles), the THF was used in an amount of 180 ml instead of 270 mland the isopropyl chloride was used in an amount of 34.6 g (0.44 moles)instead of 51.8 g (0.66 moles). Thereby, there was obtained a THFsolution of isopropyl magnesium chloride.

On the other hand, 29.9 g (0.2 moles) of methyltrichlorosilane was usedin place of tetrachlorosilane as used in Example 3 (b) and was reactedwith methanol in the same manner as in Example 3(b). There was thusobtained a THF solution of methylmethoxydichlorosilane.

The THF solution of isopropyl magnesium chloride as obtained above wasadded dropwise to the solution of methylmethoxydichlorosilane asobtained above, in the same manner as in Example 3(c), to effect theGrignard reaction. The resulting Grignard reaction solution waspost-treated similarly as in Example 3(c) with a saturated aqueousammonium chloride solution in a reduced amount of 80 ml instead of the120 ml as used in Example 3(c). The organic layer was separated and wassubjected to a fractional distillation under a reduced pressure, therebyto afford 26 g of diisopropylmethylmethoxysilane as a fraction boilingat 55° C.-56° C./43 mmHg (yield; 78%).

EXAMPLE 8

The metallic magnesium used in Example 5 was used in a reduced amount of10.7 g (0.44 moles) instead of 16.0 g (0.66 moles), and the THF was usedin a reduced amount of 180 ml instead of 270 ml, and the sec-butylchloride was used in a reduced amount of 40.8 g (0.44 moles). Thesereaction components were reacted in the same manner as in Example 3 (a),thereby to obtain a THF solution of sec-butyl magnesium chloride.

The sec-butyl magnesium chloride as prepared above was added dropwise tothe methylmethoxydichlorosilane solution as obtained in Example 7, inthe same manner as in Example 3(c), to effect the Grignard reaction. Theresulting Grignard reaction solution was post-treated with the saturatedaqueous ammonium chloride solution as used in Example 3(c) in a reducedamount of 80 ml, instead of the 120 ml. The organic layer was separatedand was subjected to a fractional distillation, thereby to afford 31 gof di-sec-butyl methylmethoxysilane as a fraction boiling at 76° C.-78°C./16 mmHg (yield; 80%).

EXAMPLE 9

The metallic magnesium as used in Example 6 was used in a reduced amountof 10.7 g (0.44 moles) instead of 16.0 g (0.66 moles), and the THF wasused in a reduced amount of 180 ml instead of 270 ml, and the cyclohexylchloride was used in a reduced amount of 52.2 g (0.44 moles) instead of78.3 g (0.66 moles). The reaction components were reacted in the samemanner as in Example 6, thereby to obtain a THF solution of cyclohexylmagnesium chloride.

The THF solution of cyclohexyl magnesium chloride as prepared above wasadded dropwise to the methylmethoxydichlorosilane solution obtained inExample 7, in the same manner as in Example 3(c), to effect the Grignardreaction. The post-treatment of the resulting Grignard reaction solutionwas carried out in the same manner as in Example 3 (c), except that thesaturated aqueous ammonium chloride solution used in Example 3 (c), wasused in a reduced amount of 80 ml instead of 120 ml. The organic layerwas separated and was fractionally distilled under a reduced pressure,thereby to afford 39 g of dicyclohexylmethylmethoxysilane as a fractionboiling at 128° C.-129° C./7 mm Hg (yield; 80%).

EXAMPLE 10

(a) Preparation of a Grignard Reagent

A 200 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 5.3 g (0.22 moles) ofmetallic magnesium, 90 ml of tetrahydrofuran (THF) and a small amount ofiodine. To the resulting mixture was added dropwise 17.3 g (0.22 moles)of isopropyl chloride under a nitrogen gas atmosphere at 40° C.-50° C.over 1 hour. Then, the resulting reaction mixture was heated understirring at 50° C. for 1 hour, thereby to obtain a THF solution ofisopropyl magnesium chloride (Grignard reagent).

(b) Preparation of an Organo-substituted-mono Alkoxy-chlorosilane byDisproportionation Reaction

A 500 ml-capacity, four-necked flask was charged with 18.5 g (0.1 moles)of diisopropyldichlorosilane and 17.6 g (0.1 moles) ofdiisopropyldimethoxysilane, and the resulting mixture was stirred at 20°C.-30° C. for 1 hour. There occurred a disproportionation reaction, thusgiving a mixture comprising diisopropylmethoxychlorosilane, theunreacted diisopropyldichlorosilane and the unreacteddiisopropyldimethoxysilane.

(c) Grignard Reaction

To the mixture of the silanes containing diisopropylmethoxychlorosilaneas obtained from the disproportionation reaction in (b) above, was added150 ml of toluene to dissolve the mixture, thereby to obtain a toluenesolution of the said silane mixture. The THF solution of isopropylmagnesium chloride (Grignard reagent) as prepared in (a) above was addeddropwise through a dropping funnel to the toluene solution of saidsilane mixture at 40° C.-50° C. over 1 hour. Then the resulting mixturewas stirred at 70° C. for 4 hours. Thus, the Grignard reagent wasreacted with the diisopropylmethoxychlorosilane contained in the saidtoluene solution, to produce triisopropylmethoxysilane. To the resultingreaction solution was added dropwise 40 ml of a saturated aqueousammonium chloride solution to dissolve the magnesium salt in the latter.The organic layer was separated from the aqueous layer and the organiclayer, was distilled to afford 28 g of triisopropylmethoxysilane as afraction boiling at 85° C.-86° C./20 mm Hg. The yield was 73%.

The following Examples 11-31 illustrate the preparation oftri-organo-monochlorosilanes by the process according to the thirdaspect of this invention.

EXAMPLE 11

A 500 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 29.3 g (0.2 moles) oftriethylmethoxysilane. To the flask was then added 400 g of 35%hydrochloric acid. The resulting mixture was stirred at 20° C. for 10hours to conduct the reaction. The resulting reaction solution wasseparated into the aqueous layer and the organic layer. The organiclayer was distilled to afford 28 g of triethylchlorosilane as a fractionboiling at 142° C.-144° C. (yield; 90%).

EXAMPLE 12

A 500 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 29.3 g (0.2 moles) oftert-butyldimethylmethoxysilane. To the flask was then added 400 g of35% hydrochloric acid, and the resulting mixture was stirred at 20° C.for 5 hours to effect the reaction. There were deposited crystals, whichcrystals were then filtered off. The crystals obtained were subjected toa distillation at atmospheric pressure to afford 29 g oftert-butyldimethylchlorosilane as a fraction boiling at 125° C. (yield;95%).

EXAMPLE 13

A 500 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 37.7 g (0.2 moles) oftriisopropylmethoxysilane. To the flask was then added 150 g of 35%hydrochloric acid, and the resulting mixture was stirred at 20° C. for10 hours to effect the reaction. The resulting reaction solution wasseparated into the aqueous layer and the organic layer. The organiclayer was distilled to afford 38 g of triisopropylchlorosilane as afraction boiling at 78° C.-80° C./10 mm Hg (yield; 99%).

EXAMPLE 14

The procedure of Example 13 was repeated except thattriisopropylmethoxysilane was replaced by 83.3 g (0.2 moles) oftriisopropyl-n-butoxysilane. The latter was reacted with 35%hydrochloric acid. There was obtained 38 g of triisopropylchlorosilane(yield; 99%).

EXAMPLE 15

(a) Preparation of a Monoalkoxytrichlorosilane

A 200 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 102 g (0.6 moles) oftetrachlorosilane (silicon tetrachloride). To the latter was then addeddropwise 44 g (0.6 moles) of n-butanol at a temperature of the resultantmixture of 10° C.-25° C. over 1 hour. The resulting reaction mixture wasthen heated under stirring at 60° C.-70° C. for 1 hour. There wasobtained a reaction solution containing n-butoxy-trichlorosilane soproduced. The reaction solution was subjected to a rectification (afractional distillation). There was thus afforded 50 g ofn-butoxytrichlorosilane as a fraction boiling at 66° C.-74° C./62 mm Hg.This product showed a purity of 98% when analyzed by a gaschromatography.

(b) Preparation of Grignard Reagent

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 16.0 g (0.66 moles) ofmetallic magnesium, 270 ml of an organic solvent, tetrahydrofuran, and asmall amount of iodine. To the resulting mixture was added dropwise 51.8g (0.66 moles) of isopropyl chloride under a nitrogen gas atmosphere at40° C.-50° C. over 1 hour. The resulting reaction mixture was thenheated at 50° C. under stirring for 1 hour, thereby to obtain a reactionsolution containing isopropyl magnesium chloride (Grignard reagent) soproduced.

(c) Grignard Reaction

To the resulting tetrahydrofuran (THF) solution of isopropyl magnesiumchloride (Grignard reagent) so obtained in (b) above was added dropwise41.5 g (0.2 moles) of n-butoxytrichlorosilane as obtained in (a) above,at 30° C.-40° C. over 1 hour. Subsequently, 150 ml of toluene was addedto the resulting reaction mixture, and the mixture so obtained wasstirred at a temperature of the mixture of 90° C. for 4 hours to conductthe Grignard reaction.

To the resultant reaction solution was added dropwise 120 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt (MgCl₂) in the latter. The aqueous layer of the resulting mixturewas separated from the organic layer, affording the organic layercontaining triisopropyl-n-butoxysilane.

(d) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

To the reaction solution containing triisopropyl-n-butoxysilane asobtained in (c) above was added 150 g of 35% hydrochloric acid. Theresultant mixture was stirred at 20° C. for 10 hours to effect thereaction. The resulting reaction solution was separated into the aqueouslayer and the organic layer. The organic layer was distilled to afford35 g of triisopropylchlorosilane as a fraction boiling at 78° C.-80°C./10 mm Hg (yield; 89%).

EXAMPLE 16

The preparation of a Grignard reagent in accordance with the procedureof Example 15(b) was repeated except that isopropyl chloride wasreplaced by 61.1 g (0.66 moles) of sec-butyl chloride. The sec-butylmagnesium chloride so produced was reacted with 41.5 g (0.2 moles) ofn-butoxy-trichlorosilane in the same manner as in Example 15(c) for theGrignard reaction. The resulting reaction solution containingtri-sec-butyl-n-butoxysilane so produced was post-treated in the samemanner as in Example 15(c) to obtain the organic layer containingtri-sec-butyl-n-butoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillationunder a reduced pressure to afford 41 g of tri-sec-butylchlorosilane asa fraction boiling at 93° C.-95° C./5 mm Hg (yield; 86%).

EXAMPLE 17

(a) Preparation of Grignard Reagent

A 500 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 16.0 g (0.66 moles) ofmetallic magnesium, 270 ml of an organic solvent, tetrahydrofuran (THF)and a small amount of iodine. To the resulting mixture was addeddropwise 51.8 g (0.66 moles) of isopropyl chloride under a nitrogen gasatmosphere over 1 hour. During the dropwise addition, the temperature ofthe reaction mixture in the flask was kept at 40° C.-50° C. Then, thereaction mixture was heated at 50° C. under stirring for 1 hour, therebyto obtain a THF solution of isopropylmagnesium chloride.

(b) Preparation of a Monoalkoxy-trichlorosilane to be Used as StartingCompound

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 34.0 g (0.2 moles) oftetrachlorosilane. There was then added dropwise 6.4 g (0.2 moles) ofmethanol over 1 hour. During the dropwise addition, the temperature ofthe reaction mixture in the flask was kept at 10° C.-25° C. Then, thereaction mixture in the flask was heated at 50° C. under stirring for 1hour. There was obtained a reaction solution containingmethoxytrichlorosilane so produced.

(c) Grignard Reaction

To the solution containing methoxytrichlorosilane, which is the reactionsolution obtained in (b) above, was added the THF solution of isopropylmagnesium chloride (Grignard reagent) as prepared in (a) above, througha dropping funnel at 30° C.-40° C. over 1 hour. To the resulting mixturewas then added 150 ml of toluene, and the mixture so obtained wasstirred at a temperature of the mixture of 90° C. for 4 hours to effectthe Grignard reaction.

To the resulting reaction solution was added dropwise 120 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. The resulting mixture was separated into the aqueous layer and theorganic layer, thus to afford the organic layer containingtriisopropylmethoxysilane.

(d) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

The triisopropylmethoxysilane in the organic layer as obtained in (c)above was reacted with 35% hydrochloric acid in the same manner as inExample 15(d). The organic layer was separated from the aqueous layerand was subjected to a fractional distillation under a reduced pressure.There was thus obtained 27 g of triisopropylchlorosilane as a fractionboiling at 78° C.-80° C./10 mm Hg (yield; 69%).

EXAMPLE 18

The procedure of Example 17(b) was repeated except that methanol used inExample 17(b) was replaced by 8.8 g (0.2 moles) of ethylene oxide. Then,34.0 g of tetrachlorosilane was reacted with ethylene oxide. Thus, therewas obtained a reaction solution containing2-chloroethoxytrichlorosilane. Subsequently, a THF solution of isopropylmagnesium chloride was added to said reaction solution and the Grignardreaction was effected as in Example 17 (c). The resulting reactionsolution was post-treated in the same manner as in Example 17(c),thereby to obtain the organic layer containingtriisopropyl-2-chloroethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillationunder a reduced pressure. There was thus afforded 28 g oftriisopropylchlorosilane as a fraction boiling at 78° C.-80° C./10 mm Hg(yield; 70%).

EXAMPLE 19

The procedure of Example 17 (a) was repeated except that isopropylchloride used in Example 17(a) was replaced by 78.3 g (0.66 moles) ofcyclohexyl chloride. Thus, a THF solution of cyclohexyl magnesiumchloride was obtained.

The THF solution of the so produced Grignard reagent was added dropwiseto the solution of methoxytrichlorosilane as prepared in Example 17(b),followed by effecting the Grignard reaction in the same manner as inExample 17 (c). The resulting Grignard reaction solution waspost-treated with a saturated aqueous ammonium chloride solution in thesame manner as in Example 17 (c), and then there was separated theorganic layer containing tricyclohexylmethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was concentrated under a reduced pressure, togive crystals. The resulting crystals were recrystallized from hexane togive 41 g of tricyclohexylchlorosilane (yield; 64%).

EXAMPLE 20

The procedure of Example 17 (a) was repeated except that isopropylchloride used in Example 17(a) was replaced by 20.4 g (0.22 moles) oftert-butyl chloride. The latter was reacted with 5.3 g (0.22 moles) ofmetallic magnesium in 90 ml of THF. There was thus obtained a THFsolution of tert-butyl magnesium chloride.

On the other hand, the procedure of Example 17(b) was repeated exceptthat tetrachlorosilane used in Example 17 (b) was replaced by 25.8 g(0.2 moles) of dimethyldichlorosilane. The latter was reacted withmethanol in the same manner as in Example 17(b). Thus, there wasobtained a solution of dimethylmethoxychlorosilane.

The THF solution of tert-butyl magnesium chloride obtained as above wasadded dropwise to the solution of dimethylmethoxychlorosilane obtainedas above, followed by effecting the Grignard reaction in the same manneras in Example 17 (c). The resulting reaction solution was post-treatedwith a saturated aqueous ammonium chloride solution in the way same asthat in Example 17(c), while the aqueous NH₄Cl solution was used in areduced amount of 40 ml, but not 120 ml. There was obtained an organiclayer containing tert-butyldimethylmethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15 (d), while an increased amount of thehydrochloric acid of 300 ml was used. The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillation atatmospheric pressure, thus to afford 15 g oftert-butyldimethylchlorosilane as a fraction boiling at 124° C.-125° C.(yield; 60%).

EXAMPLE 21

(a) Preparation of an Organo-substituted-monoalkoxysilane byDisproportionation Reaction

A 500 ml-capacity, four-necked flask was charged with 12.9 g (0.1 moles)of dimethyldichlorosilane and 12.0 g (0.1 moles) ofdimethyldimethoxysilane, and the resulting mixture was stirred at 20°C.-30° C. for 1 hour. Thus, there occurred a disproportionation reactionto produce dimethylmethoxychlorosilane, so that there was obtained asilane mixture comprising the dimethylmethoxychlorosilane, the unreacteddimethyldichlorosilane and the unreacted dimethyldimethoxysilane.

(b) Grignard Reaction

To the silane mixture comprising dimethylmethoxychlorosilane as producedby the disproportionation reaction in (a) above, was added 150 ml oftoluene to dissolve the silanes in toluene, and to give a toluenesolution of said silane mixture. To the toluene solution was addeddropwise the THF solution of tert-butyl magnesium chloride as producedin Example 20, through a dropping funnel, at 40° C.-50° C. over 1 hour.Then, the resulting mixture was stirred at 70° C. for 4 hours. TheGrignard reagent could react with dimethylmethoxychlorosilane containedin the said toluene solution, to producetert-butyldimethylmethoxysilane.

To the resulting reaction solution was added dropwise 40 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. The aqueous layer of the resulting mixture was separated from theorganic layer, thereby to obtain the organic layer containingtert-butyldimethylmethoxysilane.

(c) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

To the reaction solution containing tert-butyldimethylmethoxysilane asobtained in (b) above was added 300 g of 35% hydrochloric acid. Theresulting mixture was stirred at 20° C., for 10 hours. The resultingreaction mixture was separated into the aqueous layer and the organiclayer. The organic layer was subjected to a fractional distillation atatmospheric pressure to afford 15 g of tert-butyldimethylchlorosilane asa fraction boiling at 124° C.-125° C. (yield; 60%).

EXAMPLE 22

(a) Preparation of Grignard Reagent

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 21.4 g (0.88 moles) ofmetallic magnesium, 360 ml of an organic solvent, tetrahydrofuran, and asmall amount of iodide. To the resulting mixture was added dropwise 69.1g (0.88 moles) of isopropyl chloride under a nitrogen gas atmosphere ata temperature of the mixture of 40° C.-50° C. over 1 hour. The resultingreaction mixture was then heated under stirring at 50° C. for 1 hour, toobtain a reaction solution containing isopropyl magnesium chloride(Grignard reagent) thus produced.

(b) Preparation of a Solution of a Mixture Comprising MagnesiumAlkoxides

To the THF solution of isopropyl magnesium chloride as obtained in (a)above was added dropwise 6.4 g (0.2 moles) of methanol at a temperatureof the mixture of 20° C.-30° C. over 30 minutes. There was thus obtaineda solution of a mixture comprising methoxy magnesium chloride asproduced and the unreacted isopropyl magnesium chloride.

(c) Grignard Reaction

To the above solution of the mixture comprising isopropyl magnesiumchloride and methoxy magnesium chloride as obtained in (b) above wasadded dropwise 34.0 g (0.2 moles) of tetrachlorosilane over 1 hourthrough a dropping funnel with keeping the resultant mixture at atemperature of 30° C.-40° C. The resulting mixture was stirred at atemperature of the mixture of 75° C. for 4 hours to conduct the Grignardreaction. To the resulting Grignard reaction solution was added dropwise160 ml of a saturated aqueous ammonium chloride solution to dissolve themagnesium salt. The aqueous layer of the resulting mixture was separatedfrom the organic layer, thus to afford the organic layer containingtriisopropylmethoxysilane.

(d) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

The organic layer as obtained in (c) above was treated with 35%hydrochloric acid in the same manner as in Example 15(d). The organiclayer was separated from the aqueous layer and was subjected to afractional distillation under a reduced pressure, thus to afford 24 g oftriisopropylchlorosilane as a fraction boiling at 78° C.-80° C./10 mm Hg(yield; 60%).

EXAMPLE 23

(a) Grignard Reaction and Alkoxylation Reaction

To the THF solution of isopropyl magnesium chloride as obtained inExample 22 (a) was added dropwise 34.0 g (0.2 moles) oftetrachlorosilane through a dropping funnel at a temperature of theresultant mixture of 30° C.-40° C. over 1 hour. To the resultant mixturewas then added dropwise 6.4 g (0.2 moles) of methanol through a droppingfunnel at a temperature of the mixture of 30° C.-40° C. over 30 minutes.To the resulting mixture was then added 220 ml of toluene, and theresulting mixture was stirred at a temperature of the mixture of 90° C.for 4 hours to complete the Grignard reaction.

To the resulting reaction solution was added dropwise 160 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. The aqueous layer of the resulting mixture was separated from theorganic layer, thus to obtain the organic layer containingtriisopropylmethoxysilane.

(b) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

The organic layer obtained in (a) above was treated with 35%hydrochloric acid in the same manner as in Example 15 (d) The organiclayer was separated from the aqueous layer and was subjected to afractional distillation under a reduced pressure to afford 24 g oftriisopropylchlorosilane as a fraction boiling at 78° C.-80° C./10 mm Hg(yield; 60%).

EXAMPLE 24

Instead of methanol used in Example 22(b), 12.0 g (0.2 moles) ofisopropanol was used, and isopropanol was reacted with a THF solution ofisopropyl magnesium chloride in the same manner as in Example 22 (b).There was thus obtained a solution of a mixture comprising isopropoxymagnesium chloride so produced and the unreacted isopropyl magnesiumchloride.

The resulting solution of said mixture was reacted withtetrachlorosilane in the same manner as in Example 22(c). The resultingGrignard reaction solution was post-treated in the same manner as inExample 22(c), thus to afford the organic layer containingtriisopropylisopropoxysilane.

The organic layer thus obtained was treated with 35% hydrochloric acidin the same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillationunder a reduced pressure to afford 23 g of triisopropylchlorosilane as afraction boiling at 78° C.-80° C./10 mm Hg (yield; 58%).

EXAMPLE 25

Instead of methanol used in Example 22(b), 8.8 g (0.2 moles) of ethyleneoxide was used, and this was reacted with a THF solution of isopropylmagnesium chloride in the same manner as in Example 22(b). There wasthus obtained a solution of a mixture comprising 3-methylbutoxymagnesium chloride so produced and the unreacted isopropyl magnesiumchloride.

The resulting solution of said mixture was reacted withtetrachlorosilane in the same manner as in Example 22(c). The resultingreaction solution was post-treated in the same manner as in Example 22(c), thus to afford the organic layer containingtriisopropyl-3-methylbutoxysilane.

The organic layer thus obtained was reacted with 35% hydrochloric acidin the same manner as in Example 15(d). The organic layer, after it wasseparated from the aqueous layer, was subjected to a fractionaldistillation under a reduced pressure to afford 23 g oftriisopropylchlorosilane as a fraction boiling at 78° C.-80° C./10 mm Hg(yield; 58%).

EXAMPLE 26

Instead of isopropyl chloride used in Example 22(a), 81.5 g (0.88 moles)of sec-butyl chloride was used, and this was reacted with metallicmagnesium in THF in the same manner as in Example 22(a). There wasobtained a THF solution of sec-butyl magnesium chloride. The resultingTHF solution of sec-butyl magnesium chloride was reacted with methanolin the same manner as in Example 22(b).

Thus, there was obtained a solution of a mixture comprising methoxymagnesium chloride so produced and the unreacted sec-butyl magnesiumchloride. To this solution of said mixture was added tetrachlorosilane,and the reaction was made in the same manner as in Example 22 (c). Theresulting reaction solution was post-treated in the same manner as inExample 22(c), to afford the organic layer containingtri-sec-butylmethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillationunder a reduced pressure, to afford 26 g of tri-sec-butylchlorosilane asa fraction boiling at 93° C.-95° C./5 mm Hg (yield; 54%).

EXAMPLE 27

Instead of isopropyl chloride used in Example 22 (a), 104.4 g (0.88moles) of cyclohexyl chloride was used, and this was reacted with 16.0 gof metallic magnesium in THF in the same manner as in Example 22 (a).There was obtained a THF solution of cyclohexyl magnesium chloride.

The THF solution of cyclohexyl magnesium chloride so obtained wasreacted with tetrachlorosilane and then with methanol in the same manneras in Example 23 (a). The resulting reaction solution was post-treatedin the same manner as in Example 23(a), to obtain the organic layercontaining tricyclohexylmethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15 (d). The organic layer was separatedfrom the aqueous layer and was concentrated under a reduced pressure.The resulting crystals was recrystallized from n-hexane to afford 34 gof tricyclohexylchlorosilane (yield; 55%).

EXAMPLE 28

The THF solution of isopropyl magnesium chloride as obtained in Example17 (a) was reacted with methanol in the same manner as in Example 22(b), thereby to obtain a solution of a mixture comprising methoxymagnesium chloride so produced and the unreacted isopropyl magnesiumchloride. Instead of tetrachlorosilane used in Example 22(c), 29.9 g(0.2 moles) of methyltrichlorosilane was used, and this was added tosaid THF solution comprising methoxy magnesium chloride and theisopropyl magnesium chloride obtained as above. Then the reaction wasconducted in the same manner as in Example 22 (c). The resultingGrignard reaction solution was post-treated with the saturated aqueousammonium chloride solution same as in Example 22 (c), with using areduced amount of 120 ml (not 160 ml) of the aqueous NH₄Cl solution,thus to obtain an organic layer containingdiisopropylmethylmethoxysilane.

The resulting organic layer was treated with 35% hydrochloric acid inthe same manner as in Example 15(d). The organic layer was separatedfrom the aqueous layer and was subjected to a fractional distillationunder a reduced pressure, to afford 27 g ofdiisopropylmethylchlorosilane as a fraction boiling at 57° C.-59° C./43mm Hg (yield; 80%).

EXAMPLE 29

Instead of isopropyl chloride used in Example 17(a), 61.1 g (0.66 moles)of sec-butyl chloride was used. This was reacted with metallic magnesiumin THF in the same manner as in Example 17 (a). Thus, there was obtaineda THF solution of sec-butyl magnesium chloride. The resulting THFsolution of sec-butyl magnesium chloride so produced was reacted withmethanol in the same manner as in Example 22 (b). There was thusobtained a solution of a mixture comprising methoxy magnesium chlorideso produced and the unreacted sec-butyl magnesium chloride.

To said solution comprising methoxy magnesium chloride and sec-butylmagnesium chloride which was obtained as above, was added 29.9 g (0.2moles) of methyltrichlorosilane in place of tetrachlorosilane used inExample 22 (c). Then, the reaction was conducted in the same manner asin Example 22(c). The resulting Grignard reaction solution waspost-treated in the same manner as in Example 22(c) except that theamount of the saturated aqueous ammonium chloride solution was reducedto 120 ml from the 160 ml as used in Example 22(c). Thus, there wasobtained an organic layer containing di-sec-butylmethylmethoxysilane.

The resulting organic layer containing di-sec-butyl methylmethoxysilanewas treated with 35% hydrochloric acid in the same manner as in Example15(d). The organic layer was separated from the aqueous layer and wassubjected to a fractional distillation under a reduced pressure toafford 32 g of di-sec-butylmethylchlorosilane as a fraction boiling at78° C.-81° C./16 mm Hg (yield; 81%).

EXAMPLE 30

(a) Synthesis of a Tri-organo-mono-alkoxysilane from aTri-organo-hydrosilane Compound

A 300 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 200 g of a 28% methanolicsolution of sodium methylate. The content of the flask was heated tohave a temperature of 60° C., and into the flask was added dropwise 31.7g (0.2 moles) of triisopropylhydrosilane through a dropping funnel understirring over 30 minutes. The resulting mixture was stirred for 10 hoursunder refluxing condition. The resulting reaction solution was separatedinto the lower layer comprising mainly a methanolic solution of sodiummethylate and into the upper organic layer containing mainlytriisopropylmethoxysilane. The lower layer was separated and discured,affording the upper organic layer made of a reaction solution containingtriisopropylmethoxysilane.

(b) Synthesis of a Tri-organo-chlorosilane (by the Third Aspect Processof this Invention)

The triisopropylmethoxysilane present in the upper organic layer asobtained in (a) above was reacted with 35% hydrochloric acid in the samemanner as in Example 15(d). The organic layer in the resulting reactionsolution was then separated from the aqueous layer and was subjected toa fractional distillation under a reduced pressure, to afford 31 g oftriisopropylchlorosilane as a fraction boiling at 78° C.-80° C./10 mm Hg(yield; 80%).

EXAMPLE 31

The procedure of Example 30 (a) was repeated except thattriisopropylhydrosilane used in Example 30 (a) was replaced by 23.3 g(0.2 moles) of tert-butyldimethylhydrosilane, and the reaction withsodium mathylate was effected. Thus, there was obtained the reactionsolution containing tert-butyldimethylmethoxysilane.

To the resulting reaction solution containingtert-butyldimethylmethoxysilane was added 300 g of a 35% hydrochloricacid, and the resultant mixture was stirred at 20° C. for 10 hours.There was produced and deposited tert-butyldimethylchlorosilane ascrystals, which were then separated from the aqueous layer byfiltration. The crystals as obtained were distilled at atmosphericpressure to afford 24 g of tert-butyldimethylchlorosilane as a fractionboiling at 124° C.-125° C. (yield; 78%).

Now, Procedure (A) for practicing the fourth aspect process of thisinvention is illustrated by reference to Examples 32-39 and Example 42,and Procedure (B) for practicing the same process is also illustratedwith reference to Examples 40-41.

EXAMPLE 32

(a) Preparation of Grignard Reagent

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 21.4 g (0.88 moles) ofmetallic magnesium, 360 ml of tetrahydrofuran and a small amount ofiodine. To the resulting mixture was added dropwise 69.1 g (0.88 moles)of isopropyl chloride under a nitrogen gas atmosphere at a temperatureof the mixture of 40° C.-50° C. over 1 hour. The resulting reactionmixture was then heated at 50° C. under stirring for 1 hour, thusaffording the reaction solution containing isopropyl magnesium chloride(Grignard reagent) so produced.

(b) Preparation of a Reaction Solution Containing Methoxy MagnesiumChloride

To the tetrahydrofuran solution of isopropyl magnesium chloride (thatis, an isopropyl Grignard reagent) as obtained in (a) above, was added6.4 g (0.2 moles) of methanol dropwise at 20-30° C. over 30 minutes,followed by effecting the reaction (by Procedure (A) for practicing thefourth aspect process of this invention). There was thus obtained areaction solution containing both the remaining unreacted isopropylGrignard reagent and the so produced methoxy magnesium chloride.

(c) Grignard Reaction

To the reaction solution in tetrahydrofuran containing the isopropylGrignard reagent and methoxy magnesium chloride as obtained in (b)above, was added dropwise 34.0 g (0.2 moles) of silicon tetrachloride(that is, tetrachlorosilane) at 30° C.-40° C. over 1 hour. The resultingreaction mixture was then heated at a temperature of the mixture of 75°C. under stirring for 4 hours so as to progress the reactions betweenthe reactive components. After the finish of the reactions, theresulting reaction solution was analyzed by a gas chromatography, thusconfirming the formation of triisopropylmethoxysilane in a yield of 72%.

After the completion of the reactions, there was added dropwise 160 mlof a saturated aqueous ammonium chloride solution to the resultingreaction solution to dissolve the magnesium salt. Subsequently, theorganic layer in the reaction solution was separated from the aqueouslayer and was distilled to give a fraction boiling at 85° C.-86° C./20mm Hg. Thus, there was afforded 23 g of triisopropylmethoxysilane assaid fraction (yield; 60%).

EXAMPLE 33

Procedure of Example 32(b) was repeated except that there was used 14.8g (0.2 moles) of n-butanol instead of methanol. The tetrahydrofuransolution of isopropyl magnesium chloride (the isopropyl Grignardreagent) was reacted with n-butanol in the same manner as in Example 32(b). So, there was given the reaction solution containing the remainingunreacted isopropyl magnesium chloride and the so produced n-butoxymagnesium chloride.

Then, Grignard reaction was progressed by adding SiCl₄ to the saidreaction solution and further was effected in the same manner as inExample 32 (c). After the finish of the reaction, the resulting reactionsolution was post-treated in the same manner as in Example 32(c). Theorganic layer as separated was distilled to afford 28 g oftriisopropyl-n-butoxysilane as a fraction boiling at 98° C.-102° C./12mm Hg (yield; 59%).

EXAMPLE 34

Procedure of Example 32(b) was repeated except that there was used 8.8 g(0.2 moles) of ethylene oxide instead of methanol. Thus, thetetrahydrofuran solution of isopropyl magnesium chloride was reactedwith ethylene oxide in the same manner as in Example 32 (b). So therewas given the reaction solution containing the remaining unreactedisopropyl magnesium chloride and the so produced 3-methylbutoxymagnesium chloride.

Then, Grignard reaction was progressed by adding silicon tetrachlorideto said reaction solution and was further effected in the same manner asin Example 32 (c). After the finish of the reaction, the resultingreaction solution was post-treated in the same manner as in Example32(c). The organic layer as separated was distilled to afford 29 g oftriisopropyl-3-methylbutoxysilane as a fraction boiling at 118° C.-120°C./5 mm Hg (yield; 59%).

EXAMPLE 35

The procedure of Example 32 (a) was repeated except that there was used81.5 g (0.88 moles) of sec-butyl chloride in place of isopropylchloride. Then, sec-butyl chloride was reacted with 21.4 g (0.88 moles)of metallic magnesium in tetrahydrofuran (THF) in the same manner as inExample 32 (a). So, there was given a THF solution of sec-butylmagnesium chloride (Grignard reagent).

To the above THF solution of the Grignard reagent, methanol was addedand then the reaction was effected in the same manner as in Example 32(b), giving a reaction solution containing the remaining unreactedsec-butyl magnesium chloride and the so produced methoxy magnesiumchloride.

Then, Grignard reaction was progressed by adding silicon tetrachlorideto said reaction solution and further was effected in the same manner asin Example 32 (c). After the finish of the reaction, the resultingreaction solution was post-treated in the same manner as in Example 32(c). The organic layer as separated was distilled to afford 26 g oftri-sec-butylmethoxysilane as a fraction boiling at 89° C.-91° C./5 mmHg (yield; 55%).

EXAMPLE 36

The procedure of Example 32 (a) was repeated except that there was used104.4 g (0.88 moles) of cyclohexyl chloride in place of isopropylchloride. Then cyclohexyl chloride was reacted with 21.4 g (0.88 moles)of metallic magnesium in THF in the same manner as in Example 32(a). So,there was given a THF solution of cyclohexyl magnesium chloride(Grignard reagent).

To the above THF solution of the Grignard reagent, 14.8 g (0.2 moles) ofn-butanol was added in place of methanol used in Example 32 (b). Thereaction was further effected in the same manner as in Example 32(b).Thus there was given a reaction solution containing the remainingunreacted cyclohexyl magnesium chloride and the so produced n-butoxymagnesium chloride.

Then, Grignard reaction was progressed by adding silicon tetrachlorideto the resulting reaction solution and was further effected in the samemanner as in Example 32 (c). After the finish of the reaction, theresulting reaction solution was post-treated in the same manner as inExample 32(c). The organic layer as separated was concentrated to affordcrude crystals of tricyclohexyl-n-butoxysilane. Recrystallization fromhexane gave 40 g of tricyclohexyl-n-butoxysilane (yield; 55%).

EXAMPLE 37

The procedure of Example 32 (a) was repeated except that the amount ofmetallic magnesium used was decreased from 21.4 g (0.88 moles) to 16.0 g(0.66 moles), the amount of THF was decreased from 360 ml to 270 ml andthe amount of isopropyl chloride was decreased from 69.1 g (0.88 moles)to 51.8 g (0.66 moles). Then the metallic magnesium was reacted withisopropyl chloride in the same manner as in Example 32(a). There wasthus obtained a THF solution of isopropyl magnesium chloride (Grignardreagent).

To the above THF solution of the Grignard reagent, methanol was thenadded and the reaction was effected in the same manner as in Example32(b), giving a reaction solution containing the remaining unreactedisopropyl magnesium chloride and the so produced methoxy magnesiumchloride.

Then, Grignard reaction was progressed further by adding to saidreaction solution 29.9 g (0.2 moles) of methyltrichlorosilane, insteadof the silicon tetrachloride as used in Example 32(c). After the finishof the reaction, the resulting reaction solution was post-treated in thesame manner as in Example 32(c) except that the amount of the saturatedaqueous ammonium chloride solution used was decreased from 160 ml to 120ml. The organic layer as separated was distilled to afford 27 g ofdiisopropylmethylmethoxysilane as a fraction boiling at 55° C.-56° C./43mm Hg (yield; 81%).

EXAMPLE 38

The procedure of Example 35 was repeated except that the amount ofmetallic magnesium used was decreased from 21.4 g (0.88 moles) to 16.0 g(0.66 moles), the amount of THF was decreased from 360 ml to 270 ml andthe amount of sec-butyl chloride was decreased from 81.5 g (0.88 moles)to 61.1 g (0.66 moles). Then the metallic magnesium was reacted withsec-butyl chloride in the same manner as in Example 32(a). There wasthus obtained a THF solution of sec-butyl magnesium chloride (Grignardreagent).

To the above THF solution of the Grignard reagent of sec-butyl magnesiumchloride, methanol was then added, and the reaction was made in the samemanner as in Example 32 (b). There was thus obtained a reaction solutioncontaining the remaining unreacted sec-butyl magnesium chloride and theso produced methoxy magnesium chloride.

Then, Grignard reaction was effected further by adding to said reactionsolution 29.9 g (0.2 moles) of methyltrichlorosilane, instead of silicontetrachloride as used in Example 32 (c). After the finish of thereaction, the resulting reaction solution was post-treated in the samemanner as in Example 32(c), except that the amount of the saturatedaqueous ammonium chloride solution used was decreased from 160 ml to 120ml. The organic layer as separated was distilled to afford 32 g ofdi-sec-butylmethylmethoxysilane as a fraction boiling at 76° C.-78°C./16 mm Hg (yield; 82%).

EXAMPLE 39

The procedure of Example 36 was repeated except that the amount ofmetallic magnesium used was decreased from 21.4 g (0.88 moles) to 16.0 g(0.66 moles), the amount of THF was decreased from 360 ml to 270 ml andthe amount of cyclohexyl chloride was decreased from 104.4 g (0.88moles) to 78.3 g (0.66 moles). The reaction was effected in the samemanner as in Example 32 (a). There was thus obtained a THF solution ofcyclohexyl magnesium chloride (Grignard reagent).

To the above THF solution of the Grignard reagent, cyclohexyl magnesiumchloride, methanol was then added. The reaction was then effected in thesame manner as in Example 32(b), thus to give a reaction solutioncontaining the remaining unreacted cyclohexyl magnesium chloride and theso produced methoxy magnesium chloride.

Then, Grignard reaction was effected further by adding to said reactionsolution 29.9 g (0.2 moles) of methyltrichlorosilane, instead of thesilicon tetrachloride as used in Example 32 (c). After the finish of thereaction, the resulting reaction was post-treated in the same manner asin Example 32 (c) except that the amount of the saturated aqueousammonium chloride solution used was decreased from 160 ml to 120 ml. Theorganic layer as separated was distilled to afford 41 g ofdicyclohexylmethylmethoxysilane as a fraction boiling at 128° C.-129°C./7 mm Hg (yield; 83%).

EXAMPLE 40

To the THF solution of isopropyl magnesium chloride (Grignard reagent)used in Example 32 (a), was added dropwise 34.0 g (0.2 moles) of silicontetrachloride at 30-40° C. over 1 hour, with effecting further reaction(by Procedure B of the fourth aspect process of this invention).

To the resulting reaction mixture was then added 6.4 g (0.2 moles) ofmethanol dropwise at 30-40° C. over 30 minutes, and thus the reaction asintended was effected. The reaction solution now obtained was heated at75° C. under stirring for 4 hours so as to proceed further reaction. Theresulting reaction solution was analyzed by a gas chromatography, thusconfirming the formation of triisopropylmethoxysilane in a yield of 73%.

To the resulting reaction solution above was added dropwise 160 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. Then the organic layer as separated was distilled to afford afraction boiling at 85° C.-86° C./20 mm Hg. Thus there was obtained 23 gof triisopropylmethoxysilane (yield; 61%).

EXAMPLE 41

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 34.0 g (0.2 moles) of silicontetrachloride and 200 ml of THF. To the flask was added dropwise the THFsolution of isopropyl magnesium chloride (Grignard reagent) as used inExample 32(a), at 30-40° C. over 1 hour, with accompanying somereaction.

To the reaction mixture so obtained was then added 6.4 g (0.2 moles) ofmethanol dropwise at 30-40° C. over 30 minutes, and the reaction waseffected (by Procedure B of the fourth aspect process of thisinvention). The reaction solution now obtained was heated at 75° C.under stirring for 4 hours to proceed further reaction.

To the resulting reaction solution was added dropwise 160 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. Then the organic layer was separated and was distilled to afford afraction boiling at 85° C.-86° C./20 mm Hg. Thus, there was obtained 29g of triisopropylmethoxysilane (yield; 77%).

EXAMPLE 42

(a) Preparation of Grignard Reagent

A 500 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 11.7 g (0.48 moles) ofmetallic magnesium, 200 ml of tetrahydrofuran (THF) and a small amountof iodine. To the flask was then added dropwise 37.7 g (0.48 moles) ofisopropyl chloride at 40-50° C. under a nitrogen gas atmosphere over 1hour. Then, the reaction mixture so obtained was heated at 50° C. understirring for 1 hour, thus to effect the reaction and obtain a THFsolution of isopropyl magnesium chloride (Grignard reagent) as produced.

(b) Grignard Reaction

To the THF solution of isopropyl magnesium chloride (Grignard reagent)as obtained in (a) above, was added dropwise 34.0 g (0.2 moles) oftetrachlorosilane at 30-40° C. over 1 hour. Then the mixture so obtainedwas heated at 75° C. under stirring for 4 hours to conduct the Grignardreaction. After the finish of the reaction, the resulting reactionsolution was analyzed by a gas chromatography, confirming the formationof dichlorodiisopropylsilane in a yield of 76%.

(c) Preparation of Grignard Reagent

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 4.9 g (0.20 moles) ofmetallic magnesium, 80 ml of tetrahydrofuran (THF) and a small amount ofiodine. To the flask was then added dropwise 15.7 g (0.20 moles) ofisopropyl chloride at 40-50° C. under a nitrogen gas atmosphere over 1hour. Then, the reaction mixture so obtained was heated at 50° C. understirring for 1 hour, thus to effect the reaction and obtain a THFsolution of isopropyl magnesium chloride.

(d) Preparation of Methoxy Magnesium Chloride Solution

To the THF solution of isopropyl magnesium chloride (Grignard reagent)as obtained in (c) above, was added dropwise 6.4 g (0.2 moles) ofmethanol at 20-30° C. over 30 minutes. The reaction was effected toobtain a solution of methoxy magnesium chloride.

(e) Production of a Monoalkoxy-dialkylmonochlorosilane

To the solution of methoxy magnesium chloride as obtained in (d) above,was added dropwise the solution containing dichlorodiisopropylsilane asobtained in (b) above, at 30-40° C. over 1 hour. Then, the reactionmixture so obtained was heated at 75° C. under stirring for 4 hours toconduct the reaction. The resulting reaction solution was analyzed by agas chromatography, confirming the formation ofchlorodiisopropylmethoxysilane in a yield of 74%.

(f) Preparation of Grignard Reagent

A 200 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 4.9 g (0.20 moles) ofmetallic magnesium, 80 ml of tetrahydrofuran (THF) and a small amount ofiodine. To the flask was then added dropwise 15.7 g (0.20 moles) ofisopropyl chloride at 40-50° C. under a nitrogen gas atmosphere over 1hour. Then, the reaction mixture so obtained was heated at 50° C. understirring for 1 hour, thus to effect the reaction and obtain a THFsolution of isopropyl magnesium chloride (Grignard reagent) as produced.

(g) Grignard Reaction

To the solution containing chlorodiisopropylmethoxysilane as obtained in(e) above, was added dropwise the THF solution of isopropyl magnesiumchloride (Grignard reagent) as obtained in (f) above, at 30-40° C. over1 hour. Then the reaction mixture so obtained was heated at 75° C. understirring for 4 hours to conduct the reaction. The resulting reactionsolution was analyzed by a gas chromatography, confirming the formationof triisopropylmethoxysilane in a yield of 72%.

After the finish of the reaction, to the resulting reaction solution wasadded dropwise 160 ml of a saturated aqueous ammonium chloride solutionto dissolve the magnesium salt. Then the organic layer was separated andwas fractionally distilled under a reduced pressure to afford 23 g oftriisopropylmethoxysilane as a fraction boiling at 85° C.-86° C./20 mmHg (yield; 60%).

EXAMPLE 43

(a) Preparation of Grignard Reagent

A 200 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 9.7 g (0.40 moles) ofmetallic magnesium, 165 ml of tetrahydrofuran (THF) and a small amountof iodine. To the flask was then added dropwise 31.4 g (0.40 moles) ofisopropyl chloride at 40-50° C. under a nitrogen gas atmosphere over 1hour. Then, the reaction mixture so obtained was heated at 50° C. understirring for 1 hour, thus to effect the reaction and obtain a THFsolution of isopropyl magnesium chloride (Grignard reagent) as produced.

(b) Grignard Reaction

A one liter-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 34.0 g (0.2 moles) oftetrachlorosilane. To the latter was then added dropwise the THFsolution of isopropyl magnesium chloride (Grignard reagent) as preparedin (a) above, at 30-40° C. over 1 hour. To the mixture so obtained wasadded 150 ml of toluene. The resultant mixture was stirred at 90° C. for4 hours to conduct the Grignard reaction as intended. Thus, there wasobtained a solution containing dichlorodiisopropylsilane.

(c) Production of a Mono-alkoxy-dialkylmonochlorosilane

To the solution containing dichlorodiisopropylsilane as obtained in (b)above, was added dropwise 6.4 g (0.2 moles) of methanol at 10-25° C.over 1 hour. Then, the reaction mixture so obtained was heated at 50° C.under stirring for 1 hour, thus to effect the reaction and obtain asolution containing chlorodiisopropylmethoxysilane.

(d) Preparation of Grignard Reagent

A 200 ml-capacity, four-necked flask fitted with a stirrer, athermometer and a Dimroth was charged with 6.3 g (0.26 moles) ofmetallic magnesium, 105 ml of tetrahydrofuran (THF) and a small amountof iodine. To the flask was then added dropwise 20.4 g (0.26 moles) ofisopropyl chloride at 40-50° C. under a nitrogen gas atmosphere over 1hour. Then, the reaction mixture was so obtained heated at 50° C. understirring for 1 hour, thus to effect the reaction and obtain a THFsolution of isopropyl magnesium chloride as produced.

(e) Grignard Reaction

To the THF solution containing chlorodiisopropylmethoxysilane asobtained in (c) above, was added dropwise the THF solution of isopropylmagnesium chloride (Grignard reagent) as obtained in (d) above, at30-40° C. over 1 hour. Then, the reaction mixture so obtained was heatedat 90° C. under stirring for 4 hours to conduct further the Grignardreaction.

To the resulting reaction solution was added dropwise 120 ml of asaturated aqueous ammonium chloride solution to dissolve the magnesiumsalt. After separating the organic layer, it was fractionally distilledunder a reduced pressure to afford 27 g of triisopropylmethoxysilane asa fraction boiling at 85° C.-86° C./20 mm Hg (yield; 70%).

INDUSTRIAL APPLICABILITY

As is explained hereinbefore, according to this invention, there areprovided the novel processes for the production oftri-organo-monoalkoxysilanes which are useful in industries and alsothere is provided a novel process for the production oftri-organo-monochlorosilanes which are useful in industries. These novelprocesses provided by the first to fourth aspects of this invention areutilizable for industries.

1. A process for the production of a tri-organo-monochlorosilane of thegeneral formula (XIIa)(R¹)(R²)(R³)SiCl  (XIIa) wherein R¹, R² and R³ are the same as ordifferent from each other and each is a primary, secondary or tertiaryalkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, anaralkyl group or an aryl group, but wherein R¹, R² and R³ each and alldo not represent methyl group at the same time, or for the production ofa tri-organo monochlorosilane of the general formula (XIIb)(R¹)(R²)(R^(3a))SiCl  (XIIb) wherein R¹ and R² have the same meanings asdefined above and R^(3a) is a secondary alkyl group or a tertiary alkylgroup or a cycloalkyl group, or R^(3a) is an alkyl-substituted aromatichydrocarbon group of which the alkyl substituent is bonding to a carbonatom present in the aromatic hydrocarbon group characterized in that theprocess comprises reacting hydrochloric acid with a tri-organosilanecompound of the formula (XIa)(R¹)(R²)(R³)SiZ¹  (XIa) where R¹, R² and R³ each have the same meaningsas defined above and Z¹ is a hydrolyzable group, or with atri-organosilane compound containing the bulky hydrocarbon group R^(3a)therein and having the formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb) where R¹, R² and R^(3a) have the samemeanings as defined above and Z² is a primary or secondary alkyloxygroup, a cycloalkyloxy group or an aralkyloxy group, or Z² is a2-substituted or unsubstituted-2-chloroethoxy group of the formula (A)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, or R⁴is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxy-methylene group of the formula —CH₂—O—R⁵ where R⁵ is a straightor branched chain alkyl group of 1-20 carbon atoms or an alkenyl groupof 2-10 carbon atoms or an aryl group, thereby to produce atri-organo-monochlorosilane of the formula (XIIa) or atri-organo-monochlorosilane of the formula (XIIb).
 2. The process asclaimed in claim 1, wherein the hydrolyzable group Z¹ present in thetri-organosilane compound of the formula (XIa) is a substituted orunsubstituted alkoxy group, a cycloalkyloxy group, an aralkyloxy group,an acyloxy group, amino group, or cyano group.
 3. The process as claimedin claim 1, wherein the hydrochloric acid to be used for the reaction isin the form of an aqueous hydrogen chloride solution containing 10-37%by weight concentration of hydrogen chloride.
 4. The process as claimedin claim 1, wherein the reaction with hydrochloric acid is carried outat a temperature of −20° C. to 100° C.
 5. The process as claimed inclaim 1, wherein the tri-organosilane compound of the formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb) where the group Z² present in the formula(XIb) does not mean the 2-substituted or unsubstituted-2-chloroethoxygroup of the formula (A), which is to be used as the starting compound,is the compound which has been produced by a method comprising reactingtetrachlorosilane or a di or mono-organo-di or tri-chlorosilane of theformula (XIII)(R¹)_(x)(R²)_(y)SiCl₄−(x+y)  (XIII) wherein R¹ and R² have the samemeanings as defined in claim 1 and x and y each are an integer of 0, 1or 2, where the integers for x and y are to be within the range of0≦(x+y)≦2, with an alcohol of the formula (XIV)R⁶OH  (XIV) where R⁶ is a primary or secondary alkyl group, a cycloalkylgroup or an aralkyl group, thereby to produce an organo-unsubstituted ormono-organo or di-organo-mono (alkoxy, cycloalkyloxy or aralkyloxy)-tri,di or monochlorosilane of the formula (XVa)(R¹)x(R²)ySiCl_(3−(x+y))(OR⁶)  (XVa) where R¹, R², R⁶, x and y have thesame meanings as defined above, and then reacting the produced tri, dior monochlorosilane compound of the formula (XVa) with a Grignardreagent of the formula (XVI)(R^(3a))MgX  (XVI) where R^(3a) is a secondary alkyl group, a tertiaryalkyl group or a cycloalkyl group, or R^(3a) is an alkyl-substitutedaromatic hydrocarbon group of which the alkyl substituent is bonding toa carbon atom present in the aromatic hydrocarbon group, with saidcarbon atom being adjacent to the carbon atom of the aromatichydrocarbon group that is bonding to the magnesium atom, and X ischlorine, bromine or iodine atom.
 6. The process as claimed in claim 1,wherein the tri-organosilane compound of the formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb) which is to be used as the starting compoundis an organo-unsubstituted or mono or di-organo-mono (2-substituted orunsubstituted-2-chloroethoxy) silane of the formula(XIb-1)

where R¹, R², R^(3a) and R⁴ have the same meanings as defined in claim1, and this starting silane compound of the formula (XIb-1) is thecompound which has been produced by a method comprising reactingtetrachlorosilane or a di or mono-organo-di or trichlorosilane of theformula (XIII)(R¹)_(x)(R²)_(y)SiCl_(4−(x+y))  (XIII) where R¹ and R² have the samemeanings as defined above and x and y are the integers as defined aboveand are to be within the range of 0≦(x+y)≦2, with an alkylene oxide or aglycidylether of the formula (XVII)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, or R⁴is an alkoxymethylene group, an alkenyloxymethylene group or anaryloxymethylene group of the formula —CH₂O—R⁵ where R⁵ is a straight orbranched chain alkyl group of 1-20 carbon atoms or an alkenyl group of2-10 carbon atoms or an aryl group, thereby to produce anorgano-unsubstituted or mono-organo or di-organo-mono (2-substituted orunsubstituted-2-chloroethoxy)-tri, di or monochlorosilane of the formula(XVb)

R¹, R² and R⁴ have the same meanings as defined in claim 1, and x and yare the integers to be within the range of 0≦(x+y)≦2, and then reactingthe chlorosilane compound of the general formula (XVb) with a Grignardreagent of the formula (XVI)(R^(3a))MgX  (XVI) wherein R^(3a) is a secondary alkyl group, a tertiaryalkyl group or a cycloalkyl group as defined above, or R^(3a) is thealkyl-substituted aromatic hydrocarbon group of which the alkylsubstituent is bonding to a carbon atom present in the aromatichydrocarbon group, with said carbon atom being adjacent to the carbonatom of the aromatic hydrocarbon group that is bonding to the magnesiumatom.
 7. The process as claimed in claim 1, wherein the tri-organosilanecompound of the formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb) which is to be used as the starting compoundis the compound of the formula ( XIb) which has been produced by amethod comprising admixing an alcohol of the formula (XIV)R⁶OH  (XIV) where R⁶ is a primary or secondary alkyl group, a cycloalkylgroup or an aralkyl group or an alkylene oxide or a glycidylether of theformula (XVII)

where R⁴ is a hydrogen atom or an alkyl group of 1-8 carbon atoms, or R⁴is an alkoxymethylene group, an alkenyloxy-methylene group or anaryloxymethylene group of the formula —CH₂O—R⁵ where R⁵ is a straight orbranched chain alkyl group of 1-20 carbon atoms or an alkenyl group of2-10 carbon atoms or an aryl group with a Grignard reagent of theformula (XVI)(R^(3a))MgX  (XVI) where R^(3a) is a secondary alkyl group, a tertiaryalkyl group or a cycloalkyl group, or R^(3a) is an alkyl-substitutedaromatic hydrocarbon group of which the alkyl substituent is bonding toa carbon atom present in the aromatic hydrocarbon group, with saidcarbon atom being adjacent to the carbon atom of the aromatichydrocarbon group that is bonding to the magnesium atom, effecting theGrignard reaction, then admixing the resulting reaction mixture of theGrignard reaction with tetrachlorosilane or a di or mono-organo-di ortrichlorosilane of the formula (XIII)(R¹)_(x)(R²)ySiCl_(4−(x+y))  (XIII) where R¹ and R², as defined in claim1, are the same or different from each other and each is a primary,secondary or tertiary alkyl group, a cycloalkyl group, an alkenyl group,an alkynyl group, an aryl group or an aralkyl group, and x and y each isan integer of 0, 1 or 2, where the integers for x and y are to be in therange of 0≦(x+y)≦2, subsequently causing the reactions to be effected,and then separating from the resulting different reaction products thedesired tri-organosilane compound of the formula (XIb) shown above. 8.The process as claimed in claim 1, wherein the tri-organo-silanecompound of the formula (XIb)(R¹)(R²)(R^(3a))SiZ²  (XIb) which is to be used as the starting compoundis the compound which has been produced by a method comprising admixingthe Grignard reagent of the formula (XVI)(R^(3a))MgX  (XVI) with tetrachlorosilane or a di or mono-organo-di ortrichlorosilane of the formula (XIII)(R¹)x(R²)_(y)SiCI_(4−(x+y))  (XIII) effecting the Grignard reaction,admixing the resulting reaction mixture of the Grignard reaction with analcohol of the formula (XIV)R⁶OH  (XIV) or an alkylene oxide or a glycidylether of the formula(XVII)

causing the reactions to be effected, and then separating from theresulting different reaction products the desired tri-organosilanecompound of the formula (XIb) shown above.
 9. The process as claimed inclaim 1, wherein the tri-organosilane compound of the formula (XIa)which is to be used as the starting compound, is the tri-organo-mono(alkoxy, cycloalkyloxy or alkenyloxy) silane which is of the formula(XIa-1)(R¹)(R²)(R³)Si(OR⁶)  (XIa-1) where R¹, R² and R³, as defined in claim 1,are the same as or different from each other and each stand for aprimary, secondary or tertiary alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an aralkyl group or an aryl group, butwherein R¹, R² and R³ each and all do not represent methyl group at thesame time, and which is the silane compound of the formula (XIa-1) asproduced by a method comprising reacting a tri-organo-hydrosilanecompound of the formula (XVIII)(R¹)(R²)(R³)SiH  (XVIII) where R¹, R² and R³ have the same meanings asdefined above, with an alcohol of the formula (XIV)R⁶OH  (XIV) where R⁶ is a primary or secondary alkyl group, a cycloalkylgroup or an aralkyl group, in the presence of an alkaline catalyst. 10.The process as claimed in claim 1, wherein thetri-organo-monochlorosilane of the formula (XIIa) or (XIIb) produced istert-butyldimethylmonochlorosilane.
 11. The process as claimed in claim1, wherein the tri-organo-monochlorosilane of the formula (XIIa) or(XIIb) produced is triisopropylchlorosilane.
 12. The process as claimedin claim 1, wherein the tri-organo-monochlorosilane of the formula(XIIa) or (XIIb) produced is tri-sec-butylmonochlorosilane.
 13. Theprocess as claimed in claim 1, wherein the tri-organo-monochlorosilaneof the formula (XIIa) or (XIIb) produced istricyclohexylmonochlorosilane.